TWI542949B - Black curable composition, light-shielding color filter, light-shielding film and method for manufacturing the same, wafer level lens, and solid-state imaging device - Google Patents

Description

Black curable composition, light-shielding color filter, light-shielding film and its manufacture Method, wafer level lens and solid state imaging element

The present invention relates to a black curable composition, a light-shielding color filter, a solid-state imaging element, a wafer level lens, a light-shielding film, and a method of manufacturing the light-shielding film.

In particular, the present invention relates to a black curable composition for a wafer level lens suitable for forming a light shielding layer of a wafer level lens, wherein a plurality of lenses are disposed on a substrate; and with respect to a wafer level lens, It contains a light-shielding film obtained by using a black curable composition.

Further, the present invention relates to a black curable composition, a light-shielding film, a method of producing the same, and a solid-state photographic element.

In recent years, mobile terminals for electronic devices, such as mobile phones or personal digital assistants (PDAs), have tended to be equipped with small and low-profile photography units. The camera unit typically includes a solid state imaging element, such as a charge coupled device (CCD) image sensor or a complementary metal oxide semiconductor (CMOS) image sensor, and a lens for capturing individual images onto a solid state imaging element.

As the size and thickness of mobile terminals continue to decrease and with their widespread use, the size and thickness of the camera unit installed in the mobile terminal need to be further reduced, and the productivity thereof needs to be improved. With regard to the need, a method of mass producing a photographing unit is known, whereby a lens substrate on which a plurality of lenses are formed is formed with The sensor substrates of the plurality of solid-state imaging elements are integrally combined, and then the lens substrate and the sensor substrate are cut so that the lens and the solid-state imaging element are included in each of the cutting portions.

In addition, the method of forming a lens on a wafer enables various simple forming methods, including, for example, producing a lens only on, for example, a glass wafer, and cutting the lens according to the size of the lens that can be combined with the sensor. a method of combining with a pre-separated photographic element to produce a respective photographic unit; a method of forming a plurality of lenses with a resin using only a mold, combining the lens on the sensor substrate and then cutting; and sensible sensing The combined size of the lens cuts the lens, which in turn is combined with pre-separated photographic elements to produce a separate photographic unit.

Hereinafter, each of the plurality of lenses formed on the lens substrate is referred to as a wafer level lens, and a group of lenses (including the lens substrate) formed on the lens substrate is referred to as a wafer level lens array.

Recently, attempts have been made to use a light-shielding curable composition for, for example, a camera module member in a mobile phone. In particular, as a conventional wafer-level lens array, a wafer-level lens array in which a plurality of lenses are formed is known, which is formed by dripping a curable resin material onto a light-transmitting material such as glass. The surface of the parallel plate is formed by using a mold to harden the resin material into a prescribed shape in a state in which it is placed (see, for example, Japanese Patent No. 3926380, International Publication No. WO 2008/102648, and U.S. Patent No. 6,426,829). A light-shielding region made of a black film, a metal film, or the like can be formed to adjust the amount of light in the region other than the lens segment or at a portion of the lens of the wafer level lens. In general, a light-shielding region is formed by coating a curable light-shielding composition by photolithography or by depositing a metal.

When the photolithography method is used, a black film is formed by applying a light-shielding composition (for example, a light-blocking curable composition) onto a lens and a glass substrate, and exposing and hardening a section in which a light-shielding film is to be formed. And the alkali developer was used to remove the light-shielding composition in the unexposed section.

For the reason described above, it is important that the light-shielding film exhibits high adhesion to both the lens segment and the glass substrate, but the two requirements are extremely difficult to satisfy at the same time. In addition, as It is also important to design a light-shielding film, the developability of the unexposed section, and the adhesion of the light-shielding film in the exposed section. However, if the developability is improved so as not to leave a residue on the lens, the adhesion between the formed cured film and the lens is lowered, and thus there is a concern that the light-shielding film will be easily peeled off. On the other hand, when a part of the structure for improving the adsorption characteristics is introduced into the curable composition to improve the adhesion to the lens, the developability is lowered correspondingly, and thus the light-shielding film remains in the lens due to poor development. The problem. Therefore, it is extremely difficult to achieve compatibility between the adhesion to the lens and the developability during pattern formation.

In addition, the light-shielding film is provided in a solid-state imaging element such as a CCD image sensor or a CMOS image sensor to achieve the purpose of preventing noise generation and improving image quality.

As a composition for forming a light-shielding film of a solid-state photographic element, a black curable composition containing a black substance such as carbon black or titanium black is known.

In particular, for the purpose of achieving an improved optical density or the like, a black curable composition containing titanium black having a specific X-ray diffraction peak intensity ratio has been studied (see, for example, Japanese Patent No. 3724269 and International Publication WO) 2005/037926), and a black curable composition containing titanium black having a specific nitrogen concentration or a specific crystallite diameter (see, for example, Japanese Patent Application Laid-Open (JP-A) No. 2006-182627, JP-A No. 2006 -206891 and JP-A No. 2006-209102).

Further, a composition for forming a light-shielding film containing titanium black and a resin component has been disclosed for the purpose of obtaining a high light-shielding property with a film (see, for example, JP-A No. 2007-115921).

Further, the color filter used in the liquid crystal display element includes a light-shielding color filter called a black matrix to achieve the purpose of improving contrast by shielding light between color pixels and other purposes. In addition, the camera module including the wafer level lens formed by integrating the solid-state imaging device and the lens also has a light-shielding color filter or a light-shielding film for the purpose of preventing noise generation, improving image quality, and other purposes.

As a composition of a light-shielding color filter for forming a black matrix or solid-state photographic element of a liquid crystal display element, it is known to contain a black substance such as carbon black. Or a photosensitive resin composition of titanium black (see, for example, JP-A No. 10-246955, JP-A No. 9-54431, JP-A No. 10-46042, JP-A No. 2006-36750, and JP) -A No. 2007-115921).

The black matrix of the liquid crystal display element usually needs to exhibit the light-shielding property for the visible light region, and the light-shielding color filter of the solid-state imaging element and the light-shielding film of the wafer-level lens need to exhibit the light-shielding property for the infrared light region and the visible light region. Shading characteristics.

That is, the light-shielding color filter of the solid-state imaging element and the light-shielding film of the wafer-level lens need to block light having a wavelength of 800 nm to 1300 nm in the infrared light region and need to block light in the visible light region. Prevent noise. A light-shielding color filter for solid-state photographic elements and a wafer-level lens are formed by using a photosensitive resin composition containing a black pigment such as carbon black for use in, for example, a black matrix in a liquid crystal display element. In the case of a light-shielding film, the light-shielding property for the infrared light region is insufficient, and when it is attempted to satisfy the demand for the light-shielding property for the infrared light region, it is necessary to increase the carbon content or to thicken the black layer of the light-shielding color filter.

When the photosensitive resin composition containing carbon black is cured by exposure to ultraviolet rays or the like, the carbon black absorbs ultraviolet rays in a region of 300 nm to 500 nm. Therefore, the hardening of the photosensitive resin composition is insufficient, and a product satisfying the above requirements cannot be obtained.

Other black inorganic pigments (for example, metallic pigments containing metals such as silver or tin, or titanium black) have higher light-shielding properties for infrared light regions than carbon black, and in addition, absorb ultraviolet light having a wavelength of 300 nm to 500 nm. Less than carbon black. However, when the photosensitive resin composition containing a black inorganic pigment is hardened by ultraviolet rays, there is a problem that the hardening is insufficient and the adhesion to the substrate is low.

Recently, since solid-state photographic elements have become smaller, thinner, and more sensitive, one side of the block of the self-deflecting substrate (the ruthenium substrate has a photographic element on the other side) is incident on the 矽The demand for infrared light-shielding films on substrates is increasing. For example, a light-shielding film that blocks infrared light incident on a germanium substrate (which is also hereinafter) The demand for what is called "infrared film" is growing.

The reason for this is that the ruthenium substrate which is the base body of the solid-state photographic element exhibits high transmittance for infrared light, and further, the photographic element equipped with the solid-state photographic element is sensitive not only to visible light but also to infrared light.

In order to electrically connect to a photographic element section included on the side of the ruthenium substrate in the above-described solid-state photographic element, a method in which a solder ball electrically connected to a metal electrode formed on the other side of the ruthenium substrate is inserted is often used. And connected to the circuit substrate. In the above case, a solder resist layer is formed as a protective layer at a position other than the position where the metal electrode and the solder ball are connected to each other in the metal electrode. In this regard, the infrared-shielding film needs to have high adhesion strength with the metal electrode and needs to have high adhesion strength with the solder resist layer. The infrared ray blocking film is generally formed in a pattern shape on a metal electrode and a solder resist layer by photolithography.

In this case, since the light-shielding film (infrared light-shielding film) using carbon black has high transmittance for infrared light, the above requirements cannot be satisfied at all. Thus, a light-shielding film using titanium black or a light-shielding film using a metal pigment containing a metal such as silver or tin has low transmittance for infrared light and excellent infrared light blocking ability, and thus is suitable for satisfying the above requirements. A light-shielding film.

However, according to the study by the inventors of the present invention, it is apparent that when a light-blocking film is formed using a black curable composition containing an inorganic pigment such as titanium black, the residue derived from the black curable composition tends to remain in The outside of the region where the light-shielding film is formed. On the other hand, in order to reduce the residue, when an alkali-soluble resin is added as an additive to the black curable composition and the amount thereof is relatively high, the developability during formation of the light-shielding film can be improved and the residue can be reduced. . However, a region (step) in which the film thickness of the peripheral portion of the light-shielding film is smaller than the film thickness of the central portion of the light-shielding film is generated, and thus the light-shielding ability of the peripheral portion of the light-shielding film is lowered, and the light-shielding ability of the light-shielding film is blocked. Thereby reducing the problem. Further, when the amount of the alkali-soluble resin added is relatively high to remove the residue as described above, there is a problem that the adhesion of the light-shielding film to the substrate is lowered and thus the light-shielding film is easily peeled off. Therefore, it is difficult to provide a black curable composition for forming a light-shielding film having excellent ability to block infrared light, reducing residue, and having good adhesion to a substrate.

Further, as described above, a metallic pigment containing a metal such as silver or tin or a black curable composition containing titanium black has insufficient transmittance at a wavelength of 300 nm to 500 nm, and is compatible with a solder resist layer or The adhesion of the metal electrode is poor.

A light-shielding curable composition containing a block polymer dispersant as a dispersing agent for producing a coloring matter dispersion of a coloring pigment, a light-shielding substance or the like (see, for example, JP-A No. 2007-113000) is known. number). However, the use of a light-shielding substance to form a light-shielding film has no specific application example, and it requires development.

In view of the above, the present invention proposes the following objects.

According to a first aspect of the present invention, there is provided a black curable composition for a wafer level lens which exhibits excellent developability during pattern formation and also imparts excellent adhesion to a light-shielding film formed therefrom and a lens. .

According to a first aspect of the present invention, there is also provided a wafer level lens which allows the amount of light to be appropriately adjusted by the presence of a light-shielding film, and which can be easily manufactured.

According to a second aspect of the present invention, there is provided a black curable composition for forming a light-shielding film capable of forming a light-shielding film having excellent infrared light blocking ability, thereby being capable of reducing an unexposed area during formation of a light-shielding film The residue produced in the film has excellent adhesion to the ruthenium substrate.

According to a second aspect of the present invention, a light-shielding film having excellent infrared light blocking ability and excellent adhesion to a ruthenium substrate is provided, and a method for producing a light-shielding film having a light-shielding film obtained by the method is provided. Excellent ability to block infrared light, in which the residue generated in the unexposed area is reduced during the formation of the light-shielding film, and the light-shielding film also has an improved adhesion to the germanium substrate.

According to a second aspect of the present invention, there is provided a solid-state photographic element which exhibits a reduction in noise caused by infrared light and a reduction in noise caused by a residue, and Has a uniform film thickness.

According to a third aspect of the present invention, there is provided a black curable composition capable of forming a light-shielding film having favorable light-shielding properties for light in a wide wavelength range from a visible light region to an infrared light region and having good adhesion to a substrate. It also has high hardening sensitivity and can form a high-precision pattern.

According to a third aspect of the present invention, there is provided a light-shielding color filter for a solid-state photographic element which exhibits improved image quality with excellent precision and prevents noise generation by using the black curable composition of the present invention. Provided is a wafer level lens which allows an appropriate adjustment of the amount of light and which can be easily manufactured; and a light-shielding film for a solid-state photographic element and a method of manufacturing the same.

The inventors of the present invention have conducted extensive studies on the above-described aspects, and therefore, it has been found that the object can be attained by using a pigment dispersion liquid containing a resin having a specific structure, thereby completing the present invention.

That is, according to a first aspect of the present invention, there is provided a black curable composition for a wafer level lens comprising (A1) an inorganic pigment, (B1) having a dispersion of a phosphate group or a sulfonic acid group in a molecule Resin, (C1) polymerization initiator, and (D1) polymerizable compound.

As the inorganic pigment (A1) used herein, titanium black is preferable from the viewpoint of the transmission characteristics of the ultraviolet region and the light-shielding property for the visible region to the infrared region.

In the black curable composition, from the viewpoint of the uniformity of the formed light-shielding film, it is preferred to contain (A1) an inorganic pigment in the form of a pigment dispersion liquid, which contains a phosphate group or a sulfonate by using (B1) The acid-based dispersible resin is obtained by dispersing an inorganic pigment.

Since the black curable composition for a wafer level lens according to the first aspect of the present invention contains (A1) an inorganic pigment, and preferably contains titanium black as a light-shielding substance, it is hardened with high sensitivity while maintaining Shading characteristics, and therefore it acts as a developer A black resist with excellent resistance.

Further, in order to achieve improvement of the light-shielding effect against the visible light region, it is preferred to further add a coloring agent selected from a pigment dispersion liquid, a dye or the like containing the desired (E1) organic pigment.

In a first aspect of the present invention, there is provided a wafer level lens having a black curable composition for a wafer level lens of the present invention at a peripheral portion of a lens present on a substrate The opaque section.

In particular, the first aspect of the invention is described below.

<1> A black curable composition for a wafer level lens, comprising: (A1) an inorganic pigment; (B1) a dispersible resin having a phosphate group or a sulfonic acid group in a molecule; (C1) a polymerization initiator And (D1) a polymerizable compound.

<2> The black curable composition according to <1>, wherein the (A1) inorganic pigment comprises titanium black.

<3> A black curable composition according to <1> or <2>, which further comprises (E) an organic pigment.

The black curable composition according to any one of <1> to <3> wherein the (B1) dispersible resin comprises a monomer having a phosphate group or a sulfonic acid group (b1-1) and a weight average molecular weight of a copolymer of 1,000 to 30,000 macromonomers (b1-2).

The black curable composition according to any one of <1> to <3> wherein the (B1) dispersible resin comprises a resin represented by the following formula (I): Wherein, in the formula (I), R _A represents a molecular chain having a number average molecular weight of 500 to 30,000 and selected from a polyether or a polyester; and y represents 1 or 2.

<6> A wafer-level lens which is obtained by using a black curable composition for a wafer level lens according to any one of <1> to <5> at a peripheral portion of a lens present on a substrate. The opaque section.

The second aspect of the invention is described below.

<7> A black curable composition for forming a light-shielding film, comprising: (A2) an inorganic pigment; (B2) having at least one of a phosphate group or a sulfonic acid group in a molecule and having 10 mgKOH/ a dispersible resin having an acid value of from gram to 100 mg KOH/g; (C2) a polymerization initiator; and (D2) a polymerizable compound, wherein the light-shielding film blocks infrared light and is provided on one surface of the ruthenium substrate, The substrate has photographic element segments on opposite surfaces.

<8> A black curable composition according to <7>, wherein the (A2) inorganic pigment comprises titanium black.

<9> The black curable composition according to <7> or <8>, wherein the (B2) dispersible resin includes a monomer (b2-1) having at least one of a phosphate group or a sulfonic acid group and a weight average molecular weight It is a copolymer of a macromonomer (b2-2) of 1,000 to 30,000.

The black curable composition according to any one of <7> to <9> wherein the (B2) dispersible resin comprises a resin represented by the following formula (I):

Wherein, in the formula (I), R _A represents a molecular chain having a number average molecular weight of 500 to 30,000 and selected from a polyether or a polyester; and y represents 1 or 2.

The black curable composition according to any one of <7> to <10> wherein the (B2) dispersible resin has an acid value of from 20 mgKOH/g to 70 mgKOH/g.

The black curable composition according to any one of <7> to <11> wherein the (C2) polymerization initiator is an oxime ester compound or a hexaarylbiimidazole compound.

<13> The black curable composition according to <8>, wherein the titanium black as the (A2) inorganic pigment has an average primary particle diameter of from 30 nm to 65 nm.

<14> The black curable composition according to any one of <7> to <13> wherein the content of the (B2) dispersible resin is from 0.20 to 0.40 with respect to the mass ratio of the (A2) inorganic pigment.

<15> A light-shielding film formed on one surface of a ruthenium substrate having a photographic element region on its opposite surface, using the black curable composition according to any one of <7> to <14> segment.

<16> A method of producing a light-shielding film, comprising: Applying a black curable composition according to any one of <7> to <14> on one surface of a ruthenium substrate to form a black curable composition layer having a photographic element section on the opposite surface; The black curable composition layer is subjected to pattern exposure; and after exposure, the black curable composition layer is developed to form a pattern.

<17> A solid-state photographic element comprising a light-shielding film according to <15> on one surface of a ruthenium substrate, the ruthenium substrate having a photographic element section on its opposite surface.

<18> The solid-state photographic element according to <17>, comprising: a ruthenium substrate having a photographic element section on one surface thereof; a metal electrode provided on an opposite surface of the ruthenium substrate and electrically connected to the photographic element section; And a light-shielding film according to <15>, which is provided on a surface of the germanium substrate provided with the metal electrode, and patterned to expose at least a part of the metal electrode.

<19> The solid-state imaging element according to <18>, wherein a solder resist is provided between the metal electrode and the light-shielding film.

The third aspect of the invention is described below.

<20> A black curable composition comprising: (A3) an inorganic pigment; (B3) a chain-like resin comprising a solvent-compatible portion and a pigment-adsorbing moiety having an acid group or a base; (C3) polymerization initiation And (D3) a polymerizable compound.

<21> A black curable composition according to <20>, wherein the (A3) inorganic pigment comprises titanium black.

<22> The black curable composition according to <20> or <21>, wherein the solvent compatibility portion comprises a repeating unit in an amount of 80% by mass or more and an I/O value in the range of 0.05 to 1.50.

The black curable composition according to any one of <20> to <22> wherein the solvent compatibility portion includes a repeating unit represented by the following formula (IA) or the following formula (IB):

Wherein, in the formula (IA), R ¹ represents an alkoxy group, a cycloalkoxy group or an aryloxy group; and R ² represents a hydrogen atom, a halogen atom or an alkyl group;

Wherein, in the formula (IB), R ³ represents an aryl group; and R ⁴ represents a hydrogen atom or an alkyl group.

The black curable composition according to any one of <20> to <23> wherein the (C3) polymerization initiator is an oxime ester compound or a hexaarylbiimidazole compound.

<25> The black curable composition according to any one of <20> to <24>, further comprising (E3) an alkali-soluble resin, in addition to the (B3) chain resin.

<26> The black curable composition according to any one of <20> to <25> which further comprises (F3) an organic pigment.

<27> A black curable composition for a solid-state photographic element, which comprises the black curable composition according to any one of <20> to <26>.

<28> A light-shielding color filter for a solid-state photographic element, which comprises the black curable composition according to <27>.

<29> A solid-state photographic element comprising a light-shielding color filter for a solid-state photographic element according to <28>.

<30> A black curable composition for a wafer level lens, comprising the black curable composition according to any one of <20> to <26>.

<31> A wafer level lens comprising a light-shielding film obtained using a black curable composition according to <30> at a peripheral portion of a lens existing on a substrate.

<32> The black curable composition according to any one of <20> to <26> which is used for forming an infrared ray blocking film which blocks infrared light and is provided on one surface of the ruthenium substrate.

<33> An infrared-shielding film formed on a substrate having a photographic element segment on a surface of a ruthenium substrate having a photographic element portion and a surface on which a photographic element is provided is used.

<34> A method of producing an infrared ray blocking film, comprising: applying a black curable composition according to <32> to a surface of a ruthenium substrate having a photographic element section opposite to a surface on which the photographic element is provided Forming a photosensitive layer; patterning the photosensitive layer; and developing the photosensitive layer after exposure to form a pattern.

<35> A solid-state photographic element comprising infrared light according to <33> The film is provided on the surface of the substrate having the photographic element section on the surface opposite to the surface on which the photographic element is provided.

According to a first aspect of the present invention, there is provided a black curable composition for a wafer level lens which can form a cured film having excellent light shielding properties, which can be formed by developing residue without forming a pattern on the lens A light-shielding film having a residue of the object and having excellent adhesion to the glass substrate.

According to a first aspect of the present invention, a wafer level lens is also provided which allows the amount of light to be appropriately adjusted by the presence of a light-shielding film and which can be easily manufactured.

According to a second aspect of the present invention, there is provided a black curable composition for forming a light-shielding film which can form an amount of residue having an excellent ability to block infrared light and which is not exposed in a region during formation of the light-shielding film. A light-shielding film which has a reduced adhesion and also has excellent adhesion to the substrate.

According to a second aspect of the present invention, there is also provided a light-shielding film which has excellent infrared light-blocking ability, which can reduce the amount of residue in an unexposed area during formation of a light-shielding film, and also has excellent adhesion to a substrate. force.

According to a second aspect of the present invention, there is provided a method for producing a light-shielding film which has excellent infrared light blocking ability and thereby can reduce an amount of residue in an unexposed area during formation of a light-shielding film, It also has improved adhesion to the ruthenium substrate.

According to a second aspect of the present invention, there is provided a solid-state photographic element having reduced noise caused by infrared light and reduced noise caused by residues, and thus having a uniform film thickness.

According to the <20> of the third aspect of the present invention, there is provided a black curable composition which can form light-shielding characteristics for light in a wide wavelength range from a visible light region to an infrared light region, and has good adhesion to a substrate. The light-shielding film also has high hardening sensitivity and can form a high-precision pattern.

Further, by using the black curable composition according to the third aspect of the present invention, a light-shielding color filter for a solid-state imaging element having improved image quality due to excellent precision and preventing noise is provided. Produced; and provides a wafer level lens that allows the amount of light to be properly adjusted and can be easily fabricated.

Further, by using the black curable composition according to the third aspect of the present invention, a solid-state photographic element which reduces the amount of noise caused by infrared light is provided.

That is, according to the <28> to <29> of the third aspect of the present invention, there is provided a black curable composition for solid-state photography which can form light in a wide wavelength range from a visible light region to an infrared light region. a light-shielding color filter for a solid-state photographic element having an advantageous light-shielding property and having a good adhesion to a substrate; a light-shielding color filter for a solid-state photographic element comprising the black curable composition; A solid-state photographic element comprising a opaque color filter for a solid-state photographic element.

Further, according to the third aspect of the present invention <30> to <31>, a black curable composition for a wafer level lens which can be formed in a wide wavelength range from a visible light region to an infrared light region is provided. A light-shielding film in which light has an advantageous light-shielding property and has a good adhesion to a substrate; and a wafer-level lens having a light-shielding film obtained by using the black curable composition.

Further, according to the <32> to <35> of the third aspect of the present invention, there is provided a black curable composition for forming an infrared light-shielding effect and having excellent adhesion to both the metal electrode and the solder resist layer. An infrared-shielding film; an infrared-shielding film formed by using the black curable composition; a method for producing the same; and a solid-state image sensor having an infrared-shielding film.

A black curable composition according to a third aspect of the present invention comprises (A3) an inorganic pigment; (B3) a resin having a specific structure; (C3) a polymerization initiator; and (D3) a polymerizable compound, wherein (B3) has The resin of a specific structure contains a solvent-compatible portion and a pigment-adsorbing portion having an acid group or a base. Thus, when in solid-state photographic elements When a black curable composition is used for the light-shielding color filter, the substrate adhesion is improved. Especially in the application of wafer level lenses, the adhesion between the peripheral portion of the lens and the light-shielding film and the adhesion between the glass substrate and the light-shielding film can be simultaneously improved. Further, for the infrared ray blocking film which is applied to one surface of the ruthenium substrate to block infrared light, the adhesion to both the solder resist and the metal electrode is improved. The reason for the phenomenon is assumed to be that (B3) the solvent-compatible portion of the resin having a specific structure diffuses into the solvent and also makes the acid group or the base densely dense, and not only the adhesion to the surface of the inorganic pigment is improved but also the lens The adhesion between the peripheral portion and the glass substrate is also improved.

10‧‧‧Substrate

12‧‧‧ lens/concave lens

12a‧‧‧ lens surface

12b‧‧‧The peripheral part of the lens

14‧‧‧ opaque film

14a‧‧‧ lens aperture

14A‧‧‧Light-shielding coating

16‧‧‧ mask

20‧‧‧ convex lens

50‧‧‧Distributor

60‧‧‧Mold

62‧‧‧ concave part

70‧‧‧ mask

80‧‧‧Mold

82‧‧‧ concave section

100‧‧‧Solid photographic element substrate

110‧‧‧矽 substrate

110H‧‧‧through hole

112‧‧‧Photographic components

113‧‧‧Interlayer insulation

114‧‧‧Basic layer

115‧‧‧Color filters

115B‧‧‧Blue filter

115G‧‧‧Green Filter

115R‧‧‧Red Filter

116‧‧‧Overcoat

117‧‧‧Microlens

118‧‧‧ opaque film

122‧‧‧Insulation

123‧‧‧Metal electrode

123E‧‧‧ exposed part of metal electrode 123

124‧‧‧solder layer

124H‧‧ hole

126‧‧‧Internal electrodes

127‧‧‧Part surface electrode

200‧‧‧ camera module

221‧‧‧Adhesive

230‧‧‧ glass substrate

240‧‧‧photographic lens

241‧‧‧Adhesive

242‧‧‧Infrared cut-off filter

243‧‧‧Adhesive

244‧‧‧Shading and electronic shielding

245‧‧‧Adhesive

250‧‧‧Lens Holder

260‧‧‧ solder balls

270‧‧‧ circuit board

300‧‧‧矽 substrate

310‧‧‧Circular metal electrode

320‧‧‧ opaque film

330‧‧‧solder layer

340‧‧‧ opaque film

hυ‧‧‧External incident light

M‧‧·Molded materials

S‧‧‧ gap

1 is a plan view showing an example of a wafer level lens array.

2 is a cross-sectional view taken along line A-A of the wafer level lens array shown in FIG. 1.

Fig. 3 is a plan view showing a state in which a molding material for a lens is supplied to a substrate.

4A to 4C are views showing the order in which lenses are formed in a mold on a substrate.

5A to 5C are schematic views showing the steps of forming a light-shielding film comprising the black curable composition of the present invention in a pattern shape on a substrate on which a lens is formed.

6 is a view showing another example of the configuration of a wafer level lens array.

7A to 7C are schematic views showing another embodiment of the step of forming a light-shielding film using the black curable composition of the present invention.

8A to 8C are schematic views showing a step of molding a lens on a substrate having a light-shielding layer in a pattern shape formed of the black curable composition of the present invention.

9 is a schematic cross-sectional view showing the configuration of a camera module including a solid-state imaging element according to an example of the present invention.

Figure 10 is a schematic cross-sectional view of a solid-state photographic element according to an example of a second or third aspect of the present invention.

Figure 11 is a substrate used in Example 2-2 of the second aspect and Comparative Example 2-2 or in Examples 3-118 to 3-172 and Comparative Examples 3-7 to 3-9 of the third aspect. A schematic horizontal of A Sectional view.

FIG. 12 is a schematic cross-sectional view showing a state in which a light-shielding film is formed on a substrate A.

Figure 13 is a substrate used in Example 2-3 of the second aspect and Comparative Example 2-3 or in Examples 3-118 to 3-172 and Comparative Examples 3-7 to 3-9 of the third aspect. A schematic cross-sectional view of B.

FIG. 14 is a schematic cross-sectional view showing a state in which a light-shielding film is formed on a substrate B.

Black curable composition according to the first aspect

Hereinafter, the black curable composition according to the first aspect of the present invention will be described in detail.

The black curable composition according to the first aspect of the present invention contains (A1) an inorganic pigment, (B1) a dispersible resin having a phosphate group or a sulfonic acid group in a molecule, (C1) a polymerization initiator, and (D1) Polymerizable compound.

Hereinafter, each component contained in the black curable composition for a wafer level lens according to the first aspect of the present invention will be described in order.

(A1) inorganic pigment

As the light-shielding substance used in the first aspect of the present invention, (A1) an inorganic pigment is selected from the viewpoint of storage stability and stability. As the (A1) inorganic pigment, a pigment which absorbs ultraviolet light to infrared light is preferable, and a light-shielding property is exhibited in a region in the range of ultraviolet light to infrared light.

(A1) Examples of the inorganic pigment include a pigment containing a single metal and a pigment containing a metal compound selected from a metal oxide and a metal salt.

Specific examples thereof include zinc oxide, lead white, zinc antimony white, titanium oxide, chromium oxide, iron oxide, precipitated barium sulfate, barite powder, red lead, red iron oxide, chrome yellow, zinc yellow (zinc yellow I, zinc yellow). II), ultramarine blue, Prussian blue (potassium ferrocyanide), zircon grey, yttrium yellow, chrome titanium yellow, chrome green, peacock blue, Victorian green Victoria green), navy blue (independent of Prussian blue), vanadium zirconium blue, Chrome tin pink, manganese pink, and salmon pink.

Further, examples of the black inorganic pigment include a metal oxide and a metal nitrogen compound each containing one or two selected from the group consisting of Co, Cr, Cu, Mn, Ru, Fe, Ni, Sn, Ti, and Ag. Above metal. The substance may be used singly or in the form of a mixture of two or more of them.

In particular, the pigment may be used singly or in the form of a mixture of a plurality of substances thereof to achieve the purpose of exhibiting light-shielding properties in a wide wavelength region in the ultraviolet to infrared range.

As the inorganic pigment (A1) used in the first aspect, it is preferable that the metallic pigment or titanium black containing at least one selected from the group consisting of silver and tin is light-shielding property and hardening property, and titanium black It is optimal from the viewpoint of shading characteristics.

Titanium black as used in the present invention means black particles having a titanium atom. Low-valent titanium oxide, titanium oxynitride, and the like are preferred.

Titanium black can be used as it is, and it can also be used after surface modification to achieve improved dispersibility, aggregation inhibition, and the like. Examples of the surface modification method include a method of coating a substance selected from a group consisting of cerium oxide, titanium oxide, cerium oxide, aluminum oxide, magnesium oxide, and zirconium oxide, and may also be a water repellent material (such as JP-A Surface treatment is performed as shown in 2007-302836.

Further, in order to achieve the purpose of adjusting dispersibility, coloring properties, or the like, titanium black may contain a black pigment, or a combination of two or more black pigments, such as a composite of Cu, Fe, Mn, V, Ni, and the like. Oxide, cobalt oxide, iron oxide, carbon black or aniline black. In this case, the titanium black particles account for 50% by mass or more of the pigment.

Examples of commercially available products of titanium black include TITANIUM BLACK 10S, 12S, 13R, 13M, 13M-C, 13R, 13R-N (trade name) (all manufactured by Mitsubishi Materials Corporation) and TILACK D (trade name) (by Ako Kasei Co., Ltd.).

An example of the method for producing titanium black includes a method in which a mixture of titanium oxide and titanium metal is heated under a reducing atmosphere to carry out reduction (JP-A No. 49-5432); obtained by hydrolyzing titanium tetrachloride by high temperature Method for reducing ultrafine titanium dioxide in a reducing atmosphere containing hydrogen (JP-A No. 57-205322); method for reducing titanium dioxide or titanium hydroxide in the presence of ammonia at a high temperature (JP-A Publication No. 60-65069) No. 61-201610); and a method of depositing a vanadium compound on titanium oxide or titanium hydroxide and performing high-temperature reduction in the presence of ammonia (JP-A No. 61-201610), but is not limited to the method.

The average primary particle diameter of the titanium black particles is not particularly limited, but from the viewpoint of dispersibility and light-shielding properties, it is preferably from 3 nm to 2,000 nm, more preferably from 10 nm to 500 nm, and is most preferably It is from 10 nm to 100 nm.

The average primary particle diameter of titanium black as referred to herein can be measured by using TEM (transmission electron microscope). Specifically, the average primary particle diameter can be measured by observing the pigment powder at a magnification of 30,000 times to 100,000 times using a transmission electron microscope, and obtaining a photograph thereof; measuring the diameter of 100 initial particles; The operation is repeated at the point while changing the area of the pigment powder; and the average of the calculated results. In the present specification, the value measured by this method is used as the average initial particle diameter.

The specific surface area of titanium black is not particularly limited, but a predetermined water repellency is obtained after surface treatment of titanium black with a water repellent, and the specific surface area of titanium black measured by the BET method is preferably about 5 m 2 /g. Up to 150 square meters per gram, and more preferably from about 20 square meters per gram to 100 square meters per gram.

With respect to the particle diameter of the (A1) inorganic pigment (such as titanium black) according to the first aspect of the present invention, the average primary particle diameter is preferably from 3 nm to 2,000 nm, and in terms of dispersibility, light-shielding property and over time From the viewpoint of precipitation, the average particle diameter is preferably from 10 nm to 500 nm.

In the black curable composition according to the first aspect of the present invention, the (A1) inorganic pigment may be used singly or in combination of two or more kinds thereof. In addition, such as Hereinafter, in order to achieve the purpose of adjusting the light-shielding property or other purposes, an organic pigment, a dye or the like may be used in combination therewith if necessary.

The content of the inorganic pigment (A1) in the black curable composition is preferably from 5% by mass to 70% by mass, and more preferably from 10% by mass to 50% by mass based on the total mass of the composition.

When the (A1) inorganic pigment is incorporated into the black curable composition, the (A1) inorganic pigment is preferably blended in the form of a pigment dispersion from the viewpoint of uniformity of the obtained composition, which has been previously used. (B1) Disperse resin having a phosphate group or a sulfonic acid group in the molecule as described below.

(B1) a dispersible resin having a phosphate group or a sulfonic acid group in a molecule

Hereinafter, a dispersing resin (B1) containing phosphoric acid or a sulfonic acid according to the first aspect of the present invention will be described.

(B1) a dispersible resin having a phosphate group or a sulfonic acid group in the molecule (which is hereinafter appropriately referred to as "(B1) specific resin") in the first aspect of the invention has a phosphate group in its molecule Or a sulfonic acid group. The developability and adhesion of wafer level lenses are thus improved. This is based on the fact that the dispersible resin has a strong acid group (acid group with a low pKa) such as a phosphate group or a sulfonic acid group, and this strong acid group interacts with the molecules constituting the resin used in the lens, thereby increasing Adhesion, and on the other hand, the dispersible resin has a strong acid group which is easily dissociated in the alkali developing solution, thereby easily penetrating into the developing solution, and (A1) inorganic contained in the composition by strong adsorption with the inorganic pigment. The pigment can be removed efficiently and removed along with the development of the resin.

The (B1) specific resin used in the first aspect of the invention is not particularly limited as long as it is a resin having at least one phosphate group or sulfonic acid group at any position in the molecule. From the viewpoint of the action, specifically, the (B1) specific resin is preferably (B1-1) (b1-1) a monomer having a phosphate group or a sulfonic acid group and (b1-2) having a weight average molecular weight of 1,000. a copolymer of the above macromonomer [which is hereinafter appropriately referred to as "(B1-1) copolymer"], or (B1-2) a resin represented by the following formula (I) [which is appropriately referred to as "hereinafter" (B1-2) tree fat"].

Hereinafter, a preferred embodiment of the (B1) specific resin according to the first aspect of the present invention will be described in detail.

(B1-1) (b1-1) a copolymer of a monomer having a phosphate group or a sulfonic acid group and (b1-2) a macromonomer having a weight average molecular weight of 1,000 or more

In the first aspect of the present invention, the present invention functions because the molecule of the (B1) specific resin contains a phosphate group or a sulfonic acid group which is a strong acid group having a dissociation constant pKa of 3 or less. In order to introduce the strong acid group into the resin, a method of copolymerizing (b1-1) a monomer having a phosphate group or a sulfonic acid group is preferably employed.

Examples of the monomer having a phosphate group or a sulfonic acid group include known monomers such as a phosphate group-containing monomer such as vinylphosphonic acid; and a sulfonic acid group-containing monomer such as styrenesulfonic acid or vinylsulfonate. Acid or 2-(propylene decylamino)-2-methyl-1-propane sulfonate. The monomer can be obtained in the form of a commercially available product, and examples of the commercially available product include PHOSMER M, PHOSMER CL, PHOSMER PE, and PHOSMER PP (trade name) (all manufactured by Unichemical Co., Ltd.).

As (b1-2) a macromonomer having a weight average molecular weight of 1,000 or more which is a second copolymer component of the (B1-1) copolymer, any known macromonomer can be used.

Examples of the macromonomer (b1-2) include MACROMONOMER AA-6 (polymethyl methacrylate having a methacryl fluorenyl group as a terminal group), and AS-6 (a methacryl fluorenyl group as a terminal group) Styrene), AN-6S (copolymer of styrene and acrylonitrile having a methacryl fluorenyl group as a terminal group) and AB-6 (polybutyl acrylate having a methacryl fluorenyl group as a terminal group) For the trade name, manufactured by TOAGOSEI Co., Ltd.); PLACCEL FM5 (addition product of 5 molar equivalents of ε-caprolactone to 2-hydroxyethyl methacrylate), and FA10L (10 molar equivalents) An addition product of ε-caprolactone and 2-hydroxyethyl methacrylate) (trade name, manufactured by Daicel Chemical Industries Limited); and a polyester-based large group as described in JP-A No. 2-272009 Molecular monomer. Among them, (A1) The dispersibility and dispersion stability of the pigment dispersion liquid in which the inorganic pigment is dispersed in the (B1) specific resin and the developability indicated by the color hardening composition using the pigment dispersion liquid, based on the polymerization Ester macromonomers are especially preferred.

The macromonomer (b1-2) preferably has a weight average molecular weight of 1,000 to 30,000, more preferably 2,000 to 20,000, and most preferably 2,000 to 10,000. When the weight average molecular weight is within the above range, the solubility of the (B1-1) copolymer in a solvent is improved, and the dispersion stability is also improved.

The weight average molecular weight of the (B1-1) copolymer is preferably from 3,000 to 50,000, more preferably from 5,000 to 40,000, and most preferably from 7,000 to 30,000. When the weight average molecular weight is within the range, the dispersion stability and developability as well as the adhesion to the lens are improved.

(B1-1) The content of the monomer having a phosphate group or a sulfonic acid group in (b1-1) is preferably from 5% by mass to 60% by mass, more preferably from 5% by mass to 50% by mass, and most Preferably, it is 10% by mass to 40% by mass. When the content is in the range, the dispersion stability, solvent solubility, and developability of the inorganic pigment are improved by the (B1-1) copolymer, and the adhesion between the formed cured film and the lens is also improved. Improvement.

Further, the content of the (b1-2) macromonomer having a weight average molecular weight of 1,000 or more in the (B1-1) copolymer is preferably from 20% by mass to 90% by mass, more preferably from 25% by mass to 70% by mass. And preferably from 30% by mass to 60% by mass. When the content is in the above range, the dispersion stability, solvent solubility, and developability of the inorganic pigment are improved by the (B1-1) copolymer, and the adhesion between the formed cured film and the lens is also improved.

The (B1-1) copolymer may further contain another monomer as a copolymerization component to adjust solvent solubility or developability. Examples of other monomers include a carboxylic acid group-containing monomer such as (meth)acrylic acid; an aliphatic group-containing monomer such as benzyl (meth)acrylate or styrene; and an alkylene oxide group Monomer. The content of the monomer in the (B1-1) copolymer is preferably from 5% by mass to 30% by mass, and most preferably from 5% by mass to 20% by mass.

Among the (B1) specific resins used in the first aspect of the invention, the specific structure of the compound belonging to the (B1-1) copolymer is shown below ((B1-1-1) to (B1-1-) 11)) (the structure relates to a copolymer component contained in the compound), but the invention is not limited thereto.

(B1-2) a resin represented by the formula (I)

Subsequently, (B1-2) a resin which is another preferred embodiment of the (B1) specific resin used in the first aspect of the invention is described. (B1-2) The resin is a resin represented by the following formula (I):

In the formula (I), R _A represents a molecular chain selected from a polyether and a polyester having a number average molecular weight of 500 to 30,000. y represents an integer of 1 or 2. When y represents 2, a plurality of R _A may be the same or different from each other.

The (B1-2) resin represented by the formula (I) can be produced by a known method, for example, the method described in JP-A No. 3-112992, and specifically, it can be a polyether having a hydroxyl group at the terminal. And / or polyester is prepared by reacting with anhydrous phosphoric acid or polyphosphoric acid. In the case where R _A represents a polyether, as the polyether, polyethylene oxide or polypropylene oxide is preferred. In the case where R _A represents a polyester, as the polyester, a polyester formed by ring-opening polymerization of a lactone is preferred, and polycaprolactone is also preferred.

The number average molecular weight of the molecular chain represented by R _A is preferably from 500 to 30,000, more preferably from 500 to 20,000, and most preferably from 500 to 10,000.

The weight average molecular weight of the (B1-2) resin is preferably from 500 to 30,000, more preferably from 500 to 20,000, and most preferably from 500 to 10,000. When the weight average molecular weight is within the range, the dispersion stability and developability as well as the adhesion to the lens are improved.

When the (B1-2) resin is prepared according to the synthesis method, it is obtained as a mixture of a phosphoric acid monoester (in the formula (I), y=1) and a phosphoric acid diester (in the formula (I), y=2). . The ratio of phosphoric acid monoester to phosphodiester (ie, phosphoric acid monoester: phosphodiester) is preferably a molar ratio of from 95:5 to 65:35, and most preferably from 95:5 to 75:25. ratio. By setting the content ratio of the phosphoric acid monoester to the phosphoric acid diester within the above range, the dispersion stability is improved. The ratio of the presence of the phosphoric acid monoester to the phosphodiester can be determined by ³¹ P NMR spectrophotometry as described in Japanese Patent Application Laid-Open (JP-T) No. 2003-533455. Further, the ratio of presence can be controlled by changing the ratio of introduction of the polyether having a hydroxyl group at the terminal and/or the ratio of the polyester to anhydrous phosphoric acid or polyphosphoric acid during the synthesis.

In the (B1) specific resin according to the first aspect of the invention, the specific structure of the compound belonging to the (B1-2) resin is shown below, but the invention is not limited to the compound. Further, for the following specific examples, y is a mixture of 1 and 2 as described above; n represents an integer of 5 to 100; and R represents a chain alkyl group having 1 to 30 carbon atoms or has 3 to 30 carbons. A cyclic alkyl group of an atom.

Black hard for wafer level lens in accordance with a first aspect of the present invention In the chemical composition (B1), the content of the specific resin is preferably in the range of 1% by mass to 90% by mass, more preferably 3% by mass to 70% by mass based on the total solid mass of the black curable composition. Within the range, and preferably in the range of 5 mass% to 50 mass%. When the content is in the range, the dispersion stability of the pigment and the pattern formability during hardening of the film are excellent.

The black curable composition for a wafer level lens according to the first aspect of the present invention contains the (A1) inorganic pigment dispersed therein by means of (B1) a specific resin as described below. The black curable composition may further contain a pigment dispersant other than (B1) a specific resin (hereinafter referred to simply as "dispersant") as long as the effect of the present invention is not impaired. Examples of the dispersing agent to be used in combination with the (B1) specific resin include known pigment dispersing agents and surfactants, which can be appropriately selected and used.

As the dispersing agent to be used in combination with the (B1) specific resin, a polymer compound having a hetero ring in a side chain is preferred. Examples of the polymer compound include a polymer comprising a polymerized unit derived from a monomer represented by the formula (1) described in JP-A No. 2008-266627, or containing maleimide or A monomer derived from a monomer of a maleimide derivative. The pigment dispersant is specifically described in paragraphs [0020] to [0047] of JP-A No. 2008-266627, and the dispersing agent described therein is also suitable for use in the present invention.

As the other dispersible agent, any of the known compounds can be arbitrarily selected, and a commercially available dispersant or a surfactant can be used. Specific examples of the commercial product usable as the dispersant of the combination include: a cationic surfactant such as an organic siloxane polymer KP341 (trade name) (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth)acrylic acid (co)polymer POLYFLOW 75, 90, 95 (trade name) (manufactured by Kyoeisha Chemical Co., Ltd.) or W001 (trade name) (available from Yusho Co., Ltd.); nonionic surfactant, Such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, poly a diol distearate or a sorbitan fatty acid ester; an anionic surfactant such as W004, W005 or W017 (trade name) (manufactured by Yusho Co., Ltd.); Polymeric dispersants such as EFKA-46, EFKA-47, EFKA-47EA, EFKA POLYMER 100, EFKA POLYMER 400, EFKA POLYMER 401, EFKA POLYMER 450 (trade name) (manufactured by Ciba Specialty Chemicals), DISPERSE AID 6, DISPERSE AID 8. DISPERSE AID 15 or DISPERSE AID 9100 (trade name) (manufactured by San Nopco Limited); various SOLSPERSE dispersants such as SOLSPERSE 3000, 5000, 9000, 12000, 13240, 13940, 17000, 24000, 26000, 28000, 32000 or 36000 (trade name) (manufactured by The Lubrizol Corporation); ADEKA PLURONIC L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P -123 (trade name) (manufactured by Asahi Denka Company Limited); IONET S-20 (trade name) (manufactured by Sanyo Chemical Industries, Ltd.); and DISPERBYK 101, 103, 106, 108, 109, 111, 112, 116, 130, 140, 142, 162, 163, 164, 166, 167, 170, 171, 174, 176, 180, 182, 2000, 2001, 2050, 2150 (trade name) (manufactured by BYK-Chemie).

Further, other preferred examples of the combined dispersing agent include oligomers and polymers having a polar group at a molecular terminal or a side chain, such as an acrylic copolymer.

In the case where other pigment dispersant is used in combination with the (B1) specific resin, the amount of the other pigment dispersant is preferably in the range of 5 mass% to 50 mass%, and more preferably, based on the content of the specific resin (B1). It is in the range of 5 mass% to 30 mass%.

(C1) polymerization initiator

The black curable composition according to the first aspect of the present invention contains a polymerization initiator.

The photopolymerization initiator used in the black curable composition according to the first aspect of the present invention is degraded under light or heat to initiate and promote polymerization of the polymerizable compound as described below, and preferably at 300 nm. An absorption compound in the wavelength range of up to 500 nm.

Specific examples of the photopolymerization initiator include an organic halide compound, an oxadiazole compound, a carbonyl compound, a ketal compound, a benzoin compound, an organic peroxide compound, an azo compound, a coumarin compound, and a stack. a nitride compound, a metallocene compound, an organoboric acid compound, a disulfonic acid compound, an oxime ester compound, a phosphonium salt compound, a mercaptophosphine (oxide) compound, and a hexaarylbiimidazole-based compound, but less The oxime ester compound and the hexaarylbiimidazole-based compound are preferred from the viewpoint of the amount of development residue and good adhesion.

More specific examples of the photopolymerization initiator include the photopolymerization initiators described in paragraphs [0081] to [0100] of JP-A No. 2006-78749 and paragraphs [0101] to [0139].

As the suitable oxime ester compound, a known compound such as a compound known as a photopolymerization initiator of a photosensitive composition in an electronic part application or the like can be used. For example, a compound selected from the compounds described in the following publications can be used: JP-A No. 57-116047, JP-A No. 61-24558, JP-A No. 62-201859, JP- A No. 62-286961, JP-A No. 7-278214, JP-A No. 2000-80068, JP-A No. 2001-233842, JP-T No. 2004-534797, JP-T No. 2002-538241 No. 2004-359639, JP-A No. 2005-97141, JP-A No. 2005-220097, WO 2005-080337 A1, JP-T No. 2002-519732, JP-A No. 2001- 235858 and JP-A No. 2005-227525.

In general, the oxime ester compound has low absorbance in the near ultraviolet region of 365 nm or 405 nm or the like, and thus has low sensitivity, but can be increased in the near ultraviolet region by a sensitizer. Sensitive to make it highly sensitive. Furthermore, it is known that when it is desired to have a higher sensitivity in actual use, the amount of effective free radicals produced can be increased by using a co-sensitizer (such as an amine or a mercaptan) in combination.

In the present invention, even when used together with a sensitizer, an oxime ester compound having a low absorption in a near ultraviolet region of 365 nm or 405 nm or the like can be made remarkable in practical use. Higher sensitivity.

Herein, the oxime ester compound has low absorbance in a region of 380 nm to 480 nm, and is hardly colored, especially yellow, and thus, in its color filter for image display elements ( In the case of the main application of the present invention, an image with high color purity can be obtained. When the oxime ester compound is used in a color filter for color decomposition of a solid-state photographic element, which is another application, a color signal having a high resolution can be obtained, and thus the solid-state photographic element can achieve high resolution. .

As a oxime ester compound, a compound having low absorption and high decomposition efficiency in the range of 380 nm to 480 nm, or high absorbance in the range of 380 nm to 480 nm, but due to photolysis Compounds having a reduced absorbance in this region (by-products having an absorption at a short wavelength) are preferred.

In the following, specific examples of oxime ester compounds are shown.

Examples of the hexaarylbiimidazole compound include various compounds disclosed in JP-B Nos. 6-29285 and U.S. Patent Nos. 3,479,185, 4,311,783 and 4,622,286, and more specifically 2,2'-double (ortho) Chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(o-bromophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(o-, p-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(o-chlorophenyl)-4,4' ,5,5'-tetrakis(m-methoxyphenyl)biimidazole, 2,2'-bis(o-o-o-dichlorophenyl)-4,4',5,5'-tetraphenyl Imidazole, 2,2'-bis(o-nitrophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(o-methylphenyl)-4,4' , 5,5'-tetraphenylbiimidazole and 2,2'-bis(o-trifluorophenyl)-4,4',5,5'-tetraphenylbiimidazole.

In the black hardening composition according to the first aspect of the present invention, black The content of the (C1) polymerization initiator is from 0.1% by mass to 30% by mass, more preferably from 1% by mass to 25% by mass, and particularly preferably from 2% by mass to 20% by mass based on the total solid content of the color hardening composition. %. The polymerization initiator can be used singly or in combination of two or more kinds of initiators.

The black curable composition according to the first aspect of the present invention may contain a chain transfer agent depending on the polymerization initiator to be used. Examples of the chain transfer agent include an alkyl N,N-dialkylaminobenzoate and a thiol-based compound, and as a thiol-based compound, 2-mercaptobenzothiazole, 2-mercapto-1-phenylbenzene The imidazole and 3-mercaptopropionic acid may be used singly or in the form of a mixture of two or more thereof. From the standpoint of residue and adhesion, it is especially preferred to use a combination of a hexaarylbiimidazole compound and a thiol-based compound.

(D1) polymerizable compound

The black curable composition according to the first aspect of the present invention contains a polymerizable compound.

As the (D1) polymerizable compound, a compound having at least one addition-polymerizable ethylenically unsaturated group and having a boiling point of 100 ° C or more at normal pressure is preferred.

Examples of the compound having at least one addition-polymerizable ethylenically unsaturated group and having a boiling point of 100 ° C or more at normal pressure include a monofunctional acrylate or methacrylate such as polyethylene glycol mono (methyl) Acrylate, polypropylene glycol mono(meth)acrylate or phenoxyethyl (meth)acrylate; and polyfunctional acrylate or methacrylate such as polyethylene glycol di(meth)acrylate, Trimethylolethane tris(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, Diisopentaerythritol hexa(meth) acrylate, hexane diol (meth) acrylate, trimethylolpropane tris(propylene methoxypropyl) ether, tris(propylene methoxyethyl) isocyanide Uric acid ester; or addition of ethylene oxide or propylene oxide to a polyfunctional alcohol such as glycerol or trimethylolethane followed by (meth) acrylated compound; poly(methyl) acrylated Pentaerythritol or poly(meth)acrylated diisopentaerythritol; Japanese Patent Application Publication No. (JP-B) Nos. 48-41708 and 50-6034 Publication of JP-A No. 51-37193 as the Acrylic urethane as described in JP-A No. 48-64183 and JP-B Nos. 49-43191 and 52-30490; and as an epoxy resin and Epoxy acrylate of the reaction product of methyl)acrylic acid.

Further, a compound which is a photocurable monomer and an oligomer proposed in Nihon Secchaku Kyoukaishi (Journal of the Adhesion Society of Japan), Vol. 20, No. 7, pp. 300 to 308 can also be used.

Further, a compound in which ethylene oxide or propylene oxide is added with a polyfunctional alcohol and then (meth) acrylated, which is described as a formula (1) and (2) together with specific examples thereof, may also be used. JP-A No. 10-62986.

Wherein, diisopentaerythritol penta (meth) acrylate, diisopentaerythritol hexa (meth) acrylate, pentaerythritol tri (meth) acrylate, and wherein the acryl thiol group has ethylene glycol or propylene glycol The structure of the residue is preferred. It is also possible to use its oligomer type.

In addition, the urethane urethane described in JP-B No. 48-41708, JP-A No. 51-37193, and JP-B Nos. 2-32293 and No. 2-16765, and JP-B No. 58 Also preferred are urethane-based backbone-based urethane compounds as described in U.S. Pat. No. 4,498,036, the disclosure of which is incorporated herein by reference. Further, by using an addition polymerizable compound having an amine structure or a sulfide structure in a molecule as described in JP-A Nos. 63-277653, 63-260909, and 1-105238, A photopolymerizable composition excellent in photosensitivity is obtained. Examples of commercially available products include urethane oligomers UAS-10 and UAB-140 (trade name) (manufactured by Nippon Paper Industries Co., Ltd.), UA-7200 (by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (trade name) (manufactured by Nippon Kayaku Co., Ltd.) and UA-306H, UA-306T, UA-306I, AH-600, T-600, and AI-600 (by Kyoeisha Produced by Chemical Co., Ltd.).

Further, an ethylenically unsaturated compound having an acid group is also preferred. Examples of the commodity include TO-756 (a carboxyl group-containing trifunctional acrylate) and TO-13 82 (a carboxyl group-containing pentafunctional acrylate) (trade name, manufactured by Toagosei Co., Ltd.).

The polymerizable compound can be used singly or in combination of two or more kinds thereof. As a preferred combination example, a combination of two monomers having different polymerizable groups is preferred, a monomer having a polymerizable group and having a tetrafunctional or lower functionality and having a penta functionality or a higher functionality The monomer of the degree is more preferable from the viewpoint of developability/adhesion. The content of the polymerizable compound in the black curable composition is preferably from 3% by mass to 55% by mass, and more preferably from 10% by mass to 50% by mass, based on the mass of the total solid content. When the content of the (D1) polymerizable compound is within the above range, the hardening reaction proceeds sufficiently.

(E1) Other additives

In the black curable composition according to the first aspect of the present invention, in addition to the components (A1) to (D1) and the pigment dispersant, various additives may be used depending on the purpose.

(E1-1) Binder polymer

As the case may be, a binder polymer (for example, an alkali-soluble resin) may be used in the black curable composition for the purpose of improving dispersion stability, developability, film characteristics, and the like. The binder polymer can be added during dispersion or during the preparation of the hardenable composition.

Linear organic polymers are preferred for use as binders. Any known "linear organic polymer" can be used. In order to be developable with water or a weakly basic aqueous solution, a linear organic polymer which is soluble or swellable in water or a weakly basic aqueous solution is preferably selected. The selection and use of linear organic polymers can be determined not only by the application as a film former, but also by developers such as water, weakly basic aqueous solutions or organic solvents.

In linear organic polymers, [(meth)acrylic acid methacrylate/(meth)acrylic acid/other optionally addition polymerizable vinyl monomer] copolymers and [(meth)acrylic acid aryl esters/ (Meth)acrylic acid/other addition polymerizable vinyl monomer] as the case may be suitable for excellent balance between film strength, sensitivity and developability.

The weight average molecular weight of the binder polymer suitable for the black curable composition is preferably in the range of 5,000 or more, and more preferably in the range of 10,000 to 30,000. Within the range, and the number average molecular weight is preferably in the range of 1,000 or more, and more preferably in the range of 5,000 to 20,000. Further, the molecular weight of the binder polymer can be measured by the GPC method.

The content of the binder polymer is preferably from 0.1% by mass to 7.0% by mass based on the total solid content of the black curable composition of the present invention, and the viewpoint of achieving compatibility between pattern peeling and reduction of development residue is obtained. In terms of content, the content thereof is more preferably from 0.3% by mass to 6.0% by mass, and still more preferably from 1.0% by mass to 5.0% by mass.

(E1-2) Other colorants

A light-shielding substance other than a known organic pigment or inorganic pigment such as a dye may also be used in the black curable composition according to the first aspect of the present invention to exhibit desired light-shielding properties.

Examples of the coloring agent used in combination include the pigments described in paragraphs [0030] to [0044] of JP-A No. 2008-224982, CI Pigment Green 58 and CI Pigment Blue 79 (wherein the C1 substituent is exchanged) As OH), as an organic pigment, and among the colorants, examples of the pigment which is preferably used are as follows. However, the invention is not limited thereto.

CI Pigment Yellow 11, 24, 108, 109, 110, 138, 139, 150, 151, 154, 167, 180, 185; CI Pigment Orange 36; CI Pigment Red 122, 150, 171, 175, 177, 209, 224 , 242, 254, 255; CI Pigment Violet 19, 23, 29, 32; CI Pigment Blue 15:1, 15:3, 15:6, 16, 22, 60, 66; CI Pigment Green 7, 36, 37, 58; and CI Pigment Black 1, 7.

The dye which can be used as the other light-shielding substance is not particularly limited, and any dye selected from known dyes can be used. Examples of the dye include the dyes disclosed in the following patents: JP-A No. 64-90403, JP-A No. 64-91102, JP-A No. 1-94301, JP-A No. 6-11614, Japanese Patent No. 2592207, U.S. Patent No. 4,808,501, U.S. Patent No. 5,667,920, U.S. Patent No. 5,059,500, JP-A No. 5-333207, JP-A No. 6-35183, JP-A No. 6-51115, JP-A No. 6-194928, JP- A No. 8-211599, JP-A No. 4-249549, JP-A No. 10-123316, JP-A No. 11-302283, JP-A No. 7-286107, JP-A No. 2001-48823 No. 8-15522, JP-A No. 8-29771, JP-A No. 8-146215, JP-A No. 11-343437, JP-A No. 8-62416, JP-A No. 2002-14220, JP-A No. 2002-14221, JP-A No. 2002-14222, JP-A No. 2002-14223, JP-A No. 8-302224, JP-A No. 8-73758 , JP-A No. 8-179120 and JP-A No. 8-151531.

Examples of suitable dyes include pyrazole azo dyes, anilino azo dyes, triphenylmethane dyes, anthraquinone dyes, anthraquinone dyes, benzylidene dyes, oxonium dyes, pyrazolotriazole azo dyes, Pyridone azo dye, cyanine dye, phenothiazine dye, pyrrolopyrazole-imine dye, dibenzopyran dye, phthalocyanine dye, benzopyran dye, and indigo dye.

In the present invention, when combined with an inorganic pigment, a combination of compatibility between the hardening property and the light-shielding property is preferable, and a combination of the titanium black pigment and the pigment selected from the orange pigment, the red pigment, and the violet pigment is preferable, and Examples of the best combination include a combination of a titanium black pigment and a red pigment. More specific preferred examples of the red pigment used in combination include C.I. Pigment Red 254 and 255.

(E1-3) sensitizer

The black curable composition may contain a sensitizer for the purpose of improving the radical generation efficiency of the polymerization initiator and achieving a long wavelength of the sensitization wavelength.

As the sensitizer used in the present invention, a sensitizer which sensitizes the polymerization initiator used in combination by an electron transfer mechanism or an energy transfer mechanism is preferred.

Preferred examples of the sensitizer include the compounds described in paragraphs [0085] to [0098] of JP-A No. 2008-214395.

From the viewpoint of sensitivity and storage stability, the content of the sensitizer is preferably from 0.1% by mass to 30% by mass based on the total solid mass of the black curable composition. Within the range of %, more preferably in the range of 1% by mass to 20% by mass, and even more preferably in the range of 2% by mass to 15% by mass.

(E1-4) polymerization inhibitor

The light-shielding curable composition according to the first aspect of the present invention preferably contains a polymerization inhibitor to inhibit polymerization of the polymerizable compound during preparation or storage of the composition. The polymerization inhibitor may be a known thermal polymerization inhibitor, and specific examples thereof include hydroquinone, p-methoxyphenyl, di-tert-butyl-p-cresol, pyrogallol, t-butylcatechol, Phenylhydrazine, 4,4'-thiobis-(3-methyl-6-tert-butylphenol), 2,2'-methylenebis-(4-methyl-6-tert-butylphenol And N-nitrosophenylhydroxylamine ruthenium (I) salt.

The amount of the thermal polymerization inhibitor added is preferably from about 0.01% by mass to about 5% by mass based on the total solid content of the light-shielding curable composition.

The composition may optionally contain, for example, a higher fatty acid derivative such as behenic acid or decanoic acid decylamine to prevent polymerization inhibition by oxygen. When a light-shielding curable composition containing a higher fatty acid derivative is applied and dried to form a film, the higher fatty acid derivative is positioned at the surface of the coated film. The amount of the higher fatty acid derivative added is preferably from about 0.5% by mass to about 10% by mass based on the total mass of the light-shielding curable composition.

(E1-5) Adhesion Promoter

An adhesion promoter may be added to the light-shielding curable composition according to the first aspect of the present invention to improve the adhesion to the surface of a hard material such as a support. Examples of the adhesion promoter include a decane coupling agent and a titanium coupling agent.

Preferred examples of the decane coupling agent include γ-methacryloxypropyltrimethoxydecane, γ-methylpropenyloxypropyltriethoxydecane, and γ-propyleneoxypropyltrimethoxy. Decane, γ-acryloxypropyltriethoxydecane, γ-mercaptopropyltrimethoxydecane, γ-aminopropyltriethoxydecane, and phenyltrimethoxydecane. A more preferred embodiment comprises γ-methacryloxypropyltrimethoxydecane.

Addition of adhesion promoter based on the total solids content of the black curable composition The addition amount is preferably from 0.5% by mass to 30% by mass, and more preferably from 0.7% by mass to 20% by mass.

In particular, in the black curable composition of the present invention, the sensitizing colorant or the initiator may be further improved in sensitivity to effective radiation for the purpose of producing a lens on a glass substrate, or may contain a co-sensitizer In order to achieve the purpose of preventing oxygen from inhibiting polymerization of the photopolymerizable compound or other purposes. Further, known additives such as a surfactant, a diluent, a plasticizer or a sensitizer may be added as needed to improve the physical properties of the cured film.

(A1) an inorganic pigment (preferably in the form of a pigment dispersion type composition containing a pigment dispersant), (B1) a specific resin, (C1) a polymerization initiator, (D1) a polymerizable compound, and The black curable composition according to the first aspect of the present invention is prepared by adding various additives selected as appropriate to the solvent and further mixing them with an optional additive such as a surfactant.

The black curable composition according to the first aspect of the present invention has a composition as described above, and thus, by hardening it with high sensitivity, a light-shielding film having excellent light-shielding properties can be formed. Further, by using the (E-1) alkali-soluble binder polymer in combination, a highly precise light-shielding pattern can be formed, and thus, it is suitable for forming a light-shielding film for a wafer-level lens.

Black curable composition according to the second aspect

Hereinafter, the black curable composition according to the second aspect of the present invention will be described in detail.

The black curable composition according to the second aspect of the present invention is a black curable composition for forming a light-shielding film (which may be referred to as a black curable composition for a back light-shielding film in some cases), It comprises (A2) an inorganic pigment, (B2) a dispersible resin having at least one of a phosphate group and a sulfonic acid group in the molecule and having an acid value of from 10 mgKOH/g to 100 mgKOH/g, (C2) a polymerization initiator, and (D2) a polymerizable compound, and which blocks infrared light applied to one side of the substrate, the substrate having a photographic element section on the other side.

The inventors of the present invention have conducted intensive studies and thus have found A black curable composition containing (B2) a dispersible resin having at least one of a phosphate group and a sulfonic acid group in the molecule and having an acid value of from 10 mgKOH to 100 mgKOH/gm can provide a black curable composition A black curable composition for forming a light-shielding film which can form a light-shielding film having excellent infrared light blocking ability, can reduce residues on the outer side of a region where the light-shielding film is formed, and has excellent adhesion to the tantalum substrate.

The reason for the effect is not clear, but it is assumed as follows. However, the invention is not limited to the assumptions.

It is estimated that since the black curable composition of the present invention contains a strong acid group such as a phosphate group and a sulfonic acid group (an acid group having a low pKa), the acid value of the dispersible resin is 10 mgKOH/kg to 100 mg. Since KOH/gram is excessively developed during the formation of the light-shielding film, the film thickness of the peripheral portion of the light-shielding film is smaller than the film thickness of the central portion of the light-shielding film (step). Therefore, it is possible to form a light-shielding film having excellent infrared light blocking ability by using the black curable composition of the present invention.

Further, it is estimated that since the (B2) dispersible resin contains a strong acid group (such as a phosphate group and a sulfonic acid group) which is easily dissociated in an alkali developing solution, the alkali developing solution can easily infiltrate black hardening property during formation of the light-shielding film. In the composition, the permeated alkali developer is strongly adsorbed to the inorganic pigment. Therefore, when the development of the black curable composition is removed, the (A2) inorganic pigment contained in the black curable composition can be efficiently removed from the surface of the substrate. Therefore, during the formation of the light-shielding film, it is advantageous to reduce the residue in the unexposed region (which may be referred to as another formation region in some cases).

Further, it is estimated that the black curable composition contains (B2) a dispersing resin having at least one of a phosphate group and a sulfonic acid group in the molecule and having an acid value of from 10 mgKOH to 100 mgKOH/g Therefore, a strong acid group such as a phosphate group and a sulfonic acid group (an acid group having a low pKa) interacts with a molecule constituting a material used in a region in contact with the light-shielding film on the surface of the tantalum substrate, and thereby further enhances the light-shielding film. Adhesion to the substrate.

Herein, in the second aspect of the invention, "infrared light" refers to wavelength It is an area of 700 nm to 1200 nm.

Further, "blocking infrared light" means a state in which the transmittance is 3% or less over the entire wavelength range of 700 nm to 1200 nm.

Hereinafter, each component contained in the black curable composition for the backside light-shielding film according to the second aspect of the present invention will be described in order.

(A2) inorganic pigment

(A2) The inorganic pigment serves as a light-blocking substance of the black curable composition according to the second aspect of the present invention. From the viewpoint of storage stability and safety, it is preferred to use (A2) an inorganic pigment as a light-shielding substance.

As the (A2) inorganic pigment, a pigment exhibiting a light-shielding property for a region of ultraviolet light to infrared light and an ultraviolet light to infrared light absorption is preferable, and examples thereof include a pigment containing a single metal and containing a metal oxide, A pigment of a metal compound selected from a metal salt and a similar compound.

Specific examples of the (A2) inorganic pigment used in the second aspect of the present invention are the same as the specific examples of the (A1) inorganic pigment used in the first aspect of the present invention, and the details thereof (including the preferred range) The same is true.

In particular, as the (A2) inorganic pigment used in the second aspect, from the viewpoint of light-shielding properties and hardening properties, a metallic pigment or titanium black containing at least one selected from the group consisting of silver and tin is preferable. Titanium black is preferred for the viewpoint of the light-shielding property of ultraviolet light or visible light and the light-shielding property of infrared light (that is, the infrared light-shielding property).

The titanium black used in the second aspect of the present invention has the same definition as the titanium black used in the first aspect, and the details (including the preferred range) are also the same.

The average primary particle diameter of the inorganic pigment in the black curable composition according to the second aspect of the invention is particularly preferably from 30 nm to 65 nm. When the average primary particle diameter is within the above range, the coloring power is not lowered, the adhesion of the light-shielding film to the substrate is improved, and further, the step is further reduced and the residue is further suppressed.

The reason for the effect is unclear, but it is assumed that it is finer by using When titanium black is used as a black curable composition of an inorganic pigment to form a light-shielding film having a desired shape (pattern), the smoothness of the light-shielding film is improved, and thus the uneven portion is reduced, and thus, the load during development/rinsing The external force is reduced on the light-shielding film (especially the fine pattern). Further, it is estimated that when a black curable composition containing fine titanium black as an inorganic pigment is used, the alkali developing solution which permeates into the black curable composition is strongly adsorbed by the inorganic pigment during the formation of the light-shielding film, and thus It is advantageous to further reduce the residue and reduce the step (the film thickness of the peripheral portion of the light-shielding film is smaller than the film thickness of the central portion of the light-shielding film).

(B2) a dispersible resin having a phosphate group or a sulfonic acid group in the molecule

Hereinafter, a dispersing resin (B2) containing at least one of phosphoric acid and sulfonic acid according to a second aspect of the present invention (hereinafter may be referred to as "(B2) specific resin") will be described.

The (B2) specific resin contained in the black curable composition according to the second aspect of the present invention has an acid value of 10 mgKOH/g to 100 mgKOH/g and has at least a phosphate group and a sulfonic acid group. One of the dispersible resins.

Further, the "acid value" of the (B2) specific resin means the acid value at which the acid is first dissociated in the case where (B2) the specific resin has a polybasic acid such as a phosphate group.

The (B2) specific resin of the present invention has an acid value of 10 mgKOH/g to 100 mgKOH/g, and preferably 20 mgKOH/g to 70 mgKOH/g, and most preferably 30 mgKOH/g to 60 mg KOH / g.

When the acid value of the (B2) specific resin is within the above range, the adhesion of the light-shielding film to the substrate is improved, and it is advantageous to further reduce the residue outside the region where the light-shielding film is formed.

(B2) The acid value of the specific resin is adjusted to the above range by, for example, controlling (B2) the acid group content contained in the specific resin.

Further, the total amount of the phosphate group and the sulfonic acid group contained in the (B2) specific resin may be such that the acid value of the (B2) specific resin is considered to be within the range, but specifically, the specific resin The mass meter is preferably in the range of 5 mass% to 50 mass%, and more Preferably, it is in the range of 10% by mass to 30% by mass.

Further, the acid value of the (B2) specific resin is determined by, for example, neutralization titration using an aqueous sodium hydroxide solution. Specifically, titration with an aqueous solution of sodium hydroxide by means of potentiometric measurement is carried out in a solution formed by dissolving a specific resin in a solvent, and measurement of milligrams of acid contained in 1 g (B2) of a specific resin solid is determined. number. Next, by multiplying this value by 56.1 (molecular weight of KOH), the acid value of (B2) specific resin can be obtained.

The (B2) specific resin contained in the black curable composition according to the second aspect of the present invention is not particularly limited as long as it has at least one of a phosphate group and a sulfonic acid group at any position in the molecule and The resin having an acid value in the range of 10 mgKOH/g to 100 mgKOH/g may be used, but in terms of action, more specifically, it is preferably (B2-1) having a phosphoric acid group and a sulfonic acid group. a copolymer of at least one of the monomers (b2-1) and a macromonomer (b2-2) having a weight average molecular weight of 1,000 to 30,000 (which is hereinafter appropriately referred to as "(B2-1) copolymer) "), or (B2-2) a resin represented by the formula (I) (which is hereinafter appropriately referred to as "(B2-2) resin").

In the following, a more preferred embodiment of the (B2) specific resin of the present invention will be described in detail.

(B2-1) (b2-1) a copolymer having at least one of a phosphate group and a sulfonic acid group and (b2-2) a macromonomer having a weight average molecular weight of 1,000 to 30,000

In the second aspect of the present invention, the action of the present invention is because (B2) the molecule of the specific resin contains at least one of a phosphate group and a sulfonic acid group which is a strong acid group having a dissociation constant pKa of 3 or less. Be able to play. In order to introduce the strong acid group into the resin, a method of copolymerizing (b2-1) a monomer having at least one of a phosphate group and a sulfonic acid group is preferably used.

The monomer having at least one of a phosphate group and a sulfonic acid group used in the second aspect of the present invention has the same definition as the monomer having a phosphate group or a sulfonic acid group used in the first aspect of the present invention. And the details (including the preferred range) are also the same.

As (b2-2) a weight average molecular weight of 1,000 to 30,000 The submonomer which is the second copolymer component of the (B2-1) copolymer may be any known macromonomer.

The example of the (b2-2) macromonomer is the same as the example of the (b1-2) macromonomer used in the first aspect of the present invention, and the details (including the preferred range) are also the same.

(b2-2) The weight average molecular weight of the macromonomer has the same definition as the weight average molecular weight of the (b1-2) macromonomer used in the first aspect of the invention, and the details thereof (including the preferred range) The same is true.

The weight average molecular weight of the (B2-1) copolymer has the same definition as the weight average molecular weight of the (B1-1) copolymer used in the first aspect of the present invention, and the details (1 includes the preferred range) are also the same. . When the weight average molecular weight is within the above range, dispersion stability, developability, and adhesion characteristics to the ruthenium substrate are improved.

(B2-1) The content of the monomer having at least one of a phosphate group and a sulfonic acid group in (b2-1) in the copolymer and the (B1-1) copolymer used in the first aspect of the invention (b1-1) The content of the monomer having a phosphate group or a sulfonic acid group has the same definition, and the details (including the preferred range) are also the same. When the content is in the above range, the dispersion stability, solvent solubility, and developability of the inorganic pigment are improved by the (B2-1) copolymer, and the adhesion between the formed light-shielding film and the ruthenium substrate is also improved. Improvement.

Further, in the (B2-1) copolymer, the (b2-2) weight average molecular weight is 1,000 or more of the macromonomer content and the (B1-1) copolymer used in the first aspect of the invention ( B1-2) The content of the monomer having a weight average molecular weight of 1,000 or more has the same definition, and the details (including the preferred range) are also the same. When the content is in the above range, the dispersion stability, solvent solubility, and developability of the inorganic pigment are improved by the (B2-1) copolymer, and the adhesion between the formed light-shielding film and the ruthenium substrate is also improved. Improvement.

The (B2-1) copolymer may further contain another monomer as a copolymerization component to adjust solvent solubility or developability. Examples of other monomers are the same as those used for the other monomers in the first aspect, and the details thereof (including the preferred range) are also the same.

In the (B2) specific resin used in the second aspect of the invention, The specific structure of the compound of the (B2-1) copolymer is shown below ((B2-1-1) to (B2-1-18)), but the invention is not limited thereto. In the following copolymers (B2-1-1) to (B2-1-18), R represents an alkyl group.

In the (B2-1-1) copolymer to (B2-1-18) copolymer as the (B2-1) copolymer, the infrared light characteristics, the residue are reduced, the adhesion to the ruthenium substrate, and the step are From the viewpoint of reduction, the (B2-1-1) copolymer and the (B2-1-18) copolymer are preferred.

Subsequently, a (B2-2) resin which is another preferred embodiment of the (B2) specific resin used in the second aspect of the present invention is described. The (B2-2) resin has the same definition as the resin represented by the formula (I) in the first aspect of the invention (B1-2), and the details (including the preferred range) thereof are also the same.

(B2-2) The resin represented by the formula (I) can be produced by a known method which is the same as the method used in the first aspect of the invention.

In the second aspect, the number average molecular weight of the molecular chain represented by R _A in the formula (I) has the same definition as the number average molecular weight of the molecular chain represented by R _A in the first aspect, and the preferred range thereof is also the same.

The weight average molecular weight of the (B2-2) resin has the same definition as the weight average molecular weight of the (B1-2) resin used in the first aspect, and the preferred range thereof is also the same. When the weight average molecular weight is within the above range, dispersion stability, developability, and adhesion to the ruthenium substrate are improved.

In the (B2) specific resin according to the second aspect of the invention, the specific structure of the compound belonging to the (B2-2) resin is shown below, but the invention is not limited to the compound. For structural formulae (B2-2-1) to (B2-2-7), -OR _A in formula (I) is shown below. Further, for the following specific examples, y represents 1 or 2 as described above; n represents an integer of 5 to 100; R represents a chain alkyl group having 1 to 30 carbon atoms or has 3 to 30 carbon atoms. A cyclic alkyl group; m represents 1 to 50; 1 represents 1 to 50; and n represents 1 to 50.

As the specific resin (B2) in the black curable composition according to the second aspect of the present invention, in the above-described manner, the step in the light-shielding film is further reduced (the film thickness of the peripheral portion of the light-shielding film is generated) The resin represented by the formula (I) from the viewpoint of a region (step) smaller than the film thickness of the central portion of the light-shielding film and a resin ((B2-2)) ) Resin) is the best. In the black curable composition according to the second aspect of the present invention, the content of the (B2) specific resin is preferably in the range of 1% by mass to 40% by mass based on the total solid mass of the black curable composition. More preferably in the range of 3% by mass to 30% by mass, and more preferably in the range of 5% by mass to Within the range of 20% by mass. In the above range, the formability of the light-shielding film having excellent infrared light blocking ability, the reduction of the residue in the region other than the region in which the light-shielding film is formed, and the adhesion to the surface of the substrate are particularly Improved.

Further, in the black curable composition according to the second aspect of the present invention, the mass ratio of (B2) specific resin to (A2) inorganic pigment content (that is, (B2) specific resin / (A2) inorganic pigment) Preferably, it is from 0.10 to 0.50, more preferably from 0.20 to 0.40, and most preferably from 0.20 to 0.30. When the mass ratio is within the range, the suppression of the residue and the reduction of the step are excellent.

The black curable composition according to the second aspect of the present invention contains the (A2) inorganic pigment dispersed therein by means of (B2) a specific resin as described below. The black curable composition may further contain a pigment dispersant other than (B2) a specific resin (hereinafter referred to simply as "dispersant") as long as the effect of the present invention is not impaired.

Examples of the dispersant used in combination with the (B2) specific resin include the same pigment dispersant and surfactant used in combination with the (B1) specific resin in the black curable composition according to the first aspect of the present invention, and The details (including the preferred range) are also the same.

(C2) polymerization initiator

The black curable composition according to the second aspect of the present invention contains a polymerization initiator.

The photopolymerization initiator used in the black curable composition according to the second aspect of the present invention has the same definition as the photopolymerization initiator used in the first aspect of the present invention, and the details thereof (including the preferred range) The same is true.

In a second aspect of the invention, in the oxime ester-based compound, 2-(O-benzylidene fluorenyl)-1-[4-(phenylthio)phenyl]-1,2-octane The ketone, 1-(O-acetamidine)-1-[9-ethyl-6-(2-methylbenzylidenyl)-9H-indazol-3-yl]ethanone is preferred.

Further, as the photopolymerization initiator based on ruthenium, a compound represented by the following formula (1) (hereinafter also referred to as "specific ruthenium compound") is also preferable. Further, the specific hydrazine compound may be a hydrazine compound in which an oxime containing an N-O bond is an (E)-type isomerization oxime compound or (Z) a mixture of the isomeric hydrazine compound, or the (E) type isomeric hydrazine compound and the (Z) type isomeric hydrazine compound.

In the formula (1), R and B each independently represent a monovalent substituent; A represents a divalent organic group; and Ar represents an aryl group.

The monovalent group represented by R is preferably a monovalent non-metal atomic group.

Examples of monovalent non-metal radicals include alkyl, aryl, alkenyl, alkynyl, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, anthracenyl, alkoxy Carbonyl, aryloxycarbonyl, phosphonium, heterocyclic, alkylthiocarbonyl, arylthiocarbonyl, dialkylaminocarbonyl and dialkylaminothiocarbonyl. Each of them may have at least one substituent, and the substituent may be substituted with another substituent.

Examples of the substituent include: a halogen atom such as a fluorine atom, a bromine atom or an iodine atom; an alkoxy group such as a methoxy group, an ethoxy group or a tert-butoxy group; an aryloxy group such as a phenoxy group or a p-tolyloxy group An alkoxycarbonyl or aryloxycarbonyl group such as methoxycarbonyl, butoxycarbonyl or phenoxycarbonyl; a decyloxy group such as an ethoxycarbonyl group, a propenyloxy group or a benzhydryloxy group; a fluorenyl group such as B Sulfhydryl, benzhydryl, isobutyl fluorenyl, acryl fluorenyl, methacryl fluorenyl or methoxyoxazyl; alkylthio, such as methylthio or tert-butylthio; arylthio, such as phenyl sulfide Or a p-tolylthio group; an alkylamino group such as a methylamino group or a cyclohexylamino group; a dialkylamino group such as a dimethylamino group, a diethylamino group, an N-morpholinyl group or an N-piperidine group; An arylamine group such as an anilino or p-toluidine group; an alkyl group such as a methyl group, an ethyl group, a tert-butyl group or a dodecyl group; an aryl group such as a phenyl group, a p-tolyl group or a xylyl group; , cumyl, naphthyl, anthracenyl or phenanthryl; and hydroxy, carboxy, methionyl, fluorenyl, sulfonate, methylsulfonyl, p-toluenesulfonyl, amine, nitrate Base, cyano group, trifluoromethyl group, trichloromethyl group, trimethyl decyl group, Phosphonic acid group, trimethyl ammonium group, dimethyl fluorenyl group and triphenyl benzamidine methyl fluorenyl group.

The alkyl group which may have a substituent is preferably an alkyl group having 1 to 30 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, and most preferably an alkyl group having 1 to 5 carbon atoms. Examples thereof include methyl, ethyl, propyl, butyl, hexyl, octyl, decyl, dodecyl, octadecyl, isopropyl, isobutyl, t-butyl, tert-butyl , 1-ethylpentyl, cyclopentyl, cyclohexyl, trifluoromethyl, 2-ethylhexyl, benzamidine methyl, 1-naphthylmethylmethyl, 2-naphthylmethylmethyl, 4-methylthiobenzhydrylmethyl, 4-phenylthiobenzimidylmethyl, 4-dimethylaminobenzimidylmethyl, 4-cyanobenzhydrylmethyl, 4-methylbenzene Formamidine methyl, 2-methylbenzhydrylmethyl, 3-fluorobenzhydrylmethyl, 3-trifluoromethylbenzimidylmethyl and 3-nitrobenzimidylmethyl.

The aryl group which may have a substituent is preferably an aryl group having 6 to 30 carbon atoms. Examples thereof include phenyl, biphenyl, 1-naphthyl, 2-naphthyl, 9-fluorenyl, 9-phenanthryl, 1-indenyl, 5-fused tetraphenyl, 1-indenyl, 2-indole , 9-fluorenyl, triphenyl, p-tetraphenyl, o-tolyl, m-tolyl, p-tolyl, xylyl, o- cumyl, m-isopropylphenyl, p-cumyl , 2,4,6-trimethylphenyl, cyclopentadienyl, binaphthyl, tris-naphthyl, indolotetraphthyl, cycloheptatrienyl, diphenyl, dicyclopentadiene Phenyl, fluorenyl, fluorenyl, acenaphthyl, fluorenyl, fluorenyl, fluorenyl, hydrazino, hydrazinyl, fluorenyltetradecyl, fluorenyl, phenanthryl, orthotriphenyl, Mercapto, chrysenyl, condensed tetraphenyl, pleiadenyl, fluorenyl, fluorenyl, bipentyl, fused pentaphenyl, tetraphenyl, iso-hexaphenyl, thick Hexaphenyl, ruthenyl, fluorenyl, extended trinaphthyl, iso-hexaphenyl, hexaphenyl, anthracenyl and anthracenyl.

The alkenyl group which may have a substituent is preferably an alkenyl group having 2 to 10 carbon atoms. Examples thereof include a vinyl group, an allyl group, and a styryl group.

The alkynyl group which may have a substituent is preferably an alkynyl group having 2 to 10 carbon atoms. Examples thereof include an ethynyl group, a propynyl group, and a propargyl group.

The alkylsulfinyl group which may have a substituent is preferably an alkylsulfinyl group having 1 to 20 carbon atoms. Examples thereof include methylsulfinyl, ethylsulfinyl, and propyl Isosulfonyl, isopropylsulfinyl, butylsulfinyl, hexylsulfinyl, cyclohexylsulfinyl, octylsulfinyl, 2-ethylhexylsulfinyl , mercaptosulfinyl, decylsulfenyl, octadecylsulfenyl, cyanomethylsulfinyl and methoxymethylsulfinyl.

The arylsulfinyl group which may have a substituent is preferably an arylsulfinylene group having 6 to 30 carbon atoms. Examples thereof include a phenylsulfinyl group, a 1-naphthylsulfinyl group, a 2-naphthylsulfinyl group, a 2-chlorophenylsulfinyl group, a 2-methylphenylsulfinyl group, and 2 -methoxyphenylsulfinyl, 2-butoxyphenylsulfinyl, 3-chlorophenylsulfinyl, 3-trifluoromethylphenylsulfinyl, 3-cyano Phenylsulfinyl, 3-nitrophenylsulfinyl, 4-fluorophenylsulfinyl, 4-cyanophenylsulfinyl, 4-methoxyphenylsulfinyl 4-methylthiophenylsulfinyl, 4-phenylthiophenylsulfinyl and 4-dimethylaminophenylsulfinyl.

The alkylsulfonyl group which may have a substituent is preferably an alkylsulfonyl group having 1 to 20 carbon atoms. Examples thereof include methanesulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, butylsulfonyl, hexylsulfonyl, cyclohexylsulfonyl, octylsulfonyl, 2- Ethylhexylsulfonyl, fluorenylsulfonyl, decylsulfonyl, octadecylsulfonyl, cyanomethylsulfonyl, methoxymethylsulfonyl and perfluoroalkylsulfonate醯基.

The arylsulfonyl group which may have a substituent is preferably an arylsulfonyl group having 6 to 30 carbon atoms. Examples thereof include phenylsulfonyl, 1-naphthylsulfonyl, 2-naphthylsulfonyl, 2-chlorophenylsulfonyl, 2-methylphenylsulfonyl, 2-methoxyphenyl Sulfonyl, 2-butoxyphenylsulfonyl, 3-chlorophenylsulfonyl, 3-trifluoromethylphenylsulfonyl, 3-cyanophenylsulfonyl, 3-nitro Phenylsulfonyl, 4-fluorophenylsulfonyl, 4-cyanophenylsulfonyl, 4-methoxyphenylsulfonyl, 4-methylthiophenylsulfonyl, 4-benzene Alkylthiophenylsulfonyl and 4-dimethylaminophenylsulfonyl.

The fluorenyl group which may have a substituent is preferably a fluorenyl group having 2 to 20 carbon atoms. Examples thereof include an ethyl fluorenyl group, a propyl fluorenyl group, a butyl fluorenyl group, a trifluoromethylcarbonyl group, a pentamidine group, a benzamyl group, a tolylmethyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, a 4-methyl group. Thiobenzylidene, 4-phenylthiobenzhydryl, 4-dimethylaminobenzhydryl, 4-diethylaminobenzhydryl, 2- Chlorobenzyl, 2-methylbenzhydryl, 2-methoxybenzimidyl, 2-butoxybenzhydryl, 3-chlorobenzylidene, 3-trifluoromethylbenzene Formamyl, 3-cyanobenzylidene, 3-nitrobenzhydryl, 4-fluorobenzhydryl, 4-cyanobenzylidene and 4-methoxybenzimidyl.

The alkoxycarbonyl group which may have a substituent is preferably an alkoxycarbonyl group having 2 to 20 carbon atoms. Examples thereof include methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl, hexyloxycarbonyl, octyloxycarbonyl, decyloxycarbonyl, octadecyloxycarbonyl and trifluoromethoxycarbonyl.

Examples of the aryloxycarbonyl group which may have a substituent include a phenoxycarbonyl group, a 1-naphthyloxycarbonyl group, a 2-naphthyloxycarbonyl group, a 4-methylthiophenoxycarbonyl group, a 4-phenylthiophenoxy group. Carbonyl, 4-dimethylaminophenoxycarbonyl, 4-diethylaminophenoxycarbonyl, 2-chlorophenoxycarbonyl, 2-methylphenoxycarbonyl, 2-methoxyphenoxycarbonyl , 2-butoxyphenoxycarbonyl, 3-chlorophenoxycarbonyl, 3-trifluoromethylphenoxycarbonyl, 3-cyanophenoxycarbonyl, 3-nitrophenoxycarbonyl, 4- Fluorophenoxycarbonyl, 4-cyanophenoxycarbonyl and 4-methoxyphenoxycarbonyl.

The phosphinium group which may have a substituent is preferably a phosphinium group having a total of 2 to 50 carbon atoms. Examples thereof include dimethylphosphonium, diethylphosphonium, dipropylphosphonium, diphenylphosphonium, dimethoxyphosphonium, diethoxyphosphonium, diphenyl Mercaptophosphonium and bis(2,4,6-trimethylphenyl)phosphonium.

The heterocyclic group which may have a substituent is preferably an aromatic or aliphatic heterocyclic ring containing a nitrogen atom, an oxygen atom, a sulfur atom or a phosphorus atom.

Examples thereof include thienyl, benzo[b]thienyl, naphtho[2,3-b]thienyl, thioxyl, furyl, piperanyl, isobenzofuranyl, benzopyranyl, ton Xanthenyl, phenothiaphthyl, 2H-pyrrolyl, pyrrolyl, imidazolyl, pyrazolyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, pyridazinyl, isodecyl, 3H - mercapto, fluorenyl, 1H-carbazolyl, fluorenyl, 4H-quinazinyl, isoquinolinyl, quinolinyl, pyridazinyl, naphthyridinyl, quinoxalinyl, quin Oxazolinyl, cinnolinyl, acridine, 4aH-carbazolyl, oxazolyl, β-carbolinyl, phenanthryl, acridinyl, perimidinyl , morpholinyl, cyanozinyl, morphazinyl, isothiazolyl, phenothiazine, iso Oxazolyl, furazanyl, phenoxazinyl, isochroman, chromanyl, pyrrolidinyl, pyrrolinyl, imidazolidinyl, imidazolinyl, pyrazolyl, pyrazole Polinyl, piperidinyl, piperazinyl, porphyrinyl, isoindolyl, quinuclidinyl, morpholinyl and thioxanthonyl.

Examples of the alkylthiocarbonyl group which may have a substituent include a methylthiocarbonyl group, a propylthiocarbonyl group, a butylthiocarbonyl group, a hexylthiocarbonyl group, an octylthiocarbonyl group, a decylthiocarbonyl group, an octadecylthiocarbonyl group, and a trifluoro group. Methylthiocarbonyl.

Examples of the arylthiocarbonyl group which may have a substituent include 1-naphthylthiocarbonyl, 2-naphthylthiocarbonyl, 4-methylthiophenylthiocarbonyl, 4-phenylthiophenylthiocarbonyl, 4-di Methylaminophenylthiocarbonyl, 4-diethylaminophenylthiocarbonyl, 2-chlorophenylthiocarbonyl, 2-methylphenylthiocarbonyl, 2-methoxyphenylthiocarbonyl, 2-butoxy Phenylthiocarbonyl, 3-chlorophenylthiocarbonyl, 3-trifluoromethylphenylthiocarbonyl, 3-cyanophenylthiocarbonyl, 3-nitrophenylthiocarbonyl, 4-fluorophenylthiocarbonyl 4-cyanophenylthiocarbonyl and 4-methoxyphenylthiocarbonyl.

Examples of the dialkylaminocarbonyl group which may have a substituent include a dimethylaminocarbonyl group, a dimethylaminocarbonyl group, a dipropylaminocarbonyl group, and a dibutylaminocarbonyl group.

Examples of the dialkylaminothiocarbonyl group which may have a substituent include a dimethylaminothiocarbonyl group, a dipropylaminothiocarbonyl group, and a dibutylaminothiocarbonyl group.

Among them, in view of enhancing sensitivity, R in the formula (1) is more preferably a mercapto group, and specifically, an ethylidene group, a propenyl group, a benzamidine group and a tolylmethyl group are preferred.

The monovalent substituent represented by B in the formula (1) is an aryl group, a heterocyclic group, an arylcarbonyl group or a heterocyclic carbonyl group. Each of the groups may have at least one substituent, and examples of the substituent are the same as the examples of the substituents described above. The substituent may be further substituted with another substituent.

The monovalent substituent represented by B particularly preferably has any of the following structures.

In the following structures, Y, X and n have the same definitions as Y, X and n in the formula (2) described below, and the preferred ranges thereof are also the same.

Examples of the divalent organic group represented by A in the formula (1) include an alkylene group having 1 to 12 carbon atoms and having at least one substituent, a cyclohexylene group which may have at least one substituent, and may have at least An alkynyl group of a substituent. Examples of the substituent are the same as the examples of the substituents described above, and the substituent may be further substituted with another substituent.

In particular, in view of enhancing sensitivity and inhibiting coloring caused by heat aging, A in the formula (1) is preferably an unsubstituted alkyl group; and an alkyl group (for example, methyl group, ethyl group, third group) Alkyl or dodecyl) substituted alkyl; alkyl substituted by alkenyl (eg vinyl or allyl); or aryl (eg phenyl, p-tolyl, xylyl, isopropyl Alkyl, naphthyl, anthracenyl, phenanthryl or styryl) substituted alkyl.

The aryl group represented by Ar in the formula (1) is preferably an aryl group having 6 to 30 carbon atoms, and may have a substituent. Examples of the substituent are the same as the examples of the substituents described above.

Specific examples of the aryl group include a phenyl group, a biphenyl group, a 1-naphthyl group, a 2-naphthyl group, a 9-fluorenyl group, a 9-phenanthryl group, a 1-fluorenyl group, a 5-fused tetraphenyl group, a 1-decyl group, 2-indenyl, 9-fluorenyl, triphenylene, p-tetraphenyl, o-tolyl, m-tolyl, p-tolyl, xylyl, o-isopropylphenyl, m-isopropylphenyl, dimeric Propyl phenyl, 2,4,6-trimethylphenyl, cyclopentadienyl, binaphthyl, trisannaphthyl, indolotetraphthyl, cycloheptatrienyl, phenylene, dicyclopentane Dienylphenyl, fluorenyl, fluorenyl, acenoyl, fluorenyl, fluorenyl, fluorenyl, hydrazino, hydrazino, fluorenyl, fluorenyl, phenanthrenyl Phenyl, fluorenyl, benzophenanthrenyl, fused tetraphenyl, phenyl, decyl, decyl, bipentyl, fused pentaphenyl, tetraphenyl, iso-hexaphenyl, hexaphenyl , Ruji, thiol, extended trinaphthyl, iso-hexaphenyl, thick Heptaphenyl, anthracenyl and fluorenyl.

In particular, substituted or unsubstituted phenyl groups are preferred in view of enhancing sensitivity and inhibiting coloring due to heat aging.

In the formula (1), in view of sensitivity, the structure of "SAr" formed of Ar and S adjacent to Ar is preferably the structure shown below. Please note that "Me" means methyl and "Et" means ethyl.

The specific lipid compound used in the second aspect of the invention is preferably a compound represented by the following formula (2).

In the formula (2), R and X each independently represent a monovalent substituent; A and Y each independently represent a divalent organic group; Ar represents an aryl group; and n represents an integer of 0 to 5.

R, A and Ar in the formula (2) have the same definitions as R, A and Ar in the formula (1), respectively, and preferred examples thereof are also the same.

Examples of the monovalent substituent represented by X in the formula (1) include an alkyl group which may have at least one substituent, an aryl group which may have at least one substituent, an alkenyl group which may have at least one substituent, and may have at least one substitution Alkynyl group, alkoxy group which may have at least one substituent, aryloxy group which may have at least one substituent, an oxime group which may have at least one substituent, an alkylthio group which may have at least one substituent, An arylthio group having at least one substituent, an alkylsulfinyl group which may have at least one substituent, an arylsulfinyl group which may have at least one substituent, an alkylsulfonyl group which may have at least one substituent An arylsulfonyl group which may have at least one substituent, a mercapto group which may have at least one substituent, an alkoxycarbonyl group which may have at least one substituent, an amine mercapto group which may have at least one substituent, may have at least A substituent sulfonyl group, an amine group which may have at least one substituent, a phosphinium group which may have at least one substituent, a heterocyclic group which may have at least one substituent, and a halogen group. Examples of the substituent are the same as the examples of the substituents described above, and each substituent may be further substituted with another substituent.

An alkyl group, an aryl group, an alkenyl group, an alkynyl group or an alkyl group represented by X in the formula (2) Sulfosyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, fluorenyl, alkoxycarbonyl, aryloxycarbonyl, phosphonium and heterocyclic groups, respectively, and formula (1) An alkyl group, an aryl group, an alkenyl group, an alkynyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an anthracenyl group, an alkoxycarbonyl group, The aryloxycarbonyl group, the phosphonium group and the heterocyclic group have the same definition, and the preferred range thereof is also the same.

As the alkoxy group which may have a substituent, an alkoxy group having 1 to 30 carbon atoms is preferred. Examples thereof include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a second butoxy group, a third butoxy group, a pentyloxy group, an isopentyloxy group, Hexyloxy, heptyloxy, octyloxy, 2-ethylhexyloxy, nonyloxy, dodecyloxy, octadecyloxy, ethoxycarbonylmethyl, ethylhexyloxycarbonyl Oxyl, aminocarbonylmethoxy, N,N-dibutylaminocarbonylmethoxy, N-methylaminocarbonylmethoxy, N-ethylaminocarbonylmethoxy, N-octyl Aminocarbonylmethoxy, N-methyl-N-benzylaminocarbonylcarbonyl, benzyloxy and cyanomethoxy.

As the aryloxy group which may have a substituent, an aryloxy group having 6 to 30 carbon atoms is preferred. Examples thereof include phenoxy, 1-naphthyloxy, 2-naphthyloxy, 2-chlorophenoxy, 2-methylphenoxy, 2-methoxyphenoxy, 2-butoxyphenoxy , 3-chlorophenoxy, 3-trifluoromethylphenoxy, 3-cyanophenoxy, 3-nitrophenoxy, 4-fluorophenoxy, 4-cyanophenoxy, 4-methoxyphenoxy, 4-dimethylaminophenoxy, 4-methylthiophenoxy and 4-phenylthiophenoxy.

As the oxime group which may have a substituent, a decyloxy group having 2 to 20 carbon atoms is preferred. Examples thereof include ethoxylated, propyloxy, butanoxy, pentyloxy, trifluoromethylcarbonyloxy, benzylideneoxy, 1-naphthylcarbonyloxy and 2-naphthylcarbonyl Oxygen.

As the alkylthio group which may have a substituent, an alkylthio group having 1 to 20 carbon atoms is preferred. Examples thereof include methylthio, ethylthio, propylthio, isopropylthio, butylthio, hexylthio, cyclohexylthio, octylthio, 2-ethylhexylthio, Mercaptothio, decylthio, octadecylthio, cyanomethylthio and methoxymethylthio.

As the arylthio group which may have a substituent, an arylthio group having 6 to 30 carbon atoms is preferred. Examples thereof include a phenylthio group, a 1-naphthylthio group, a 2-naphthylthio group, a 2-chlorophenylthio group, a 2-methylphenylthio group, a 2-methoxyphenylthio group, and 2 -butoxyphenylthio, 3-chlorophenylthio, 3-trifluoromethylphenylthio, 3-cyanophenylthio, 3-nitrophenylthio, 4-fluorobenzene Thiothio group, 4-cyanophenylthio group, 4-methoxyphenylthio group, 4-methylthiophenylthio group, 4-phenylthiophenylthio group and 4-dimethylamino group Phenylthio.

As the amine mercapto group which may have a substituent, an amine formazan group having a total of 1 to 30 carbon atoms is preferred. Examples thereof include N-methylaminecarbamyl, N-ethylamine, mercapto, N-propylamine, mercapto, N-butylamine, N-hexylamine, N-ring Hexylamine, mercaptomethyl, N-octylamine, mercapto, N-decylamine, mercapto, N-octadecylamine, N-phenylamine, mercapto, N-2-methyl Phenylamine, mercapto, N-2-chlorophenylamine, mercapto, N-2-isopropoxyphenylamine, mercapto, N-2-(2-ethylhexyl)phenylamine , N-3-chlorophenylamine, mercapto, N-3-nitrophenylamine, mercapto, N-3-cyanophenylamine, mercapto, N-4-methoxyphenylamine Mercapto, N-4-cyanophenylamine, mercapto, N-4-methylthiophenylamine, N-4-phenylthiophenylamine, N-methyl -N-phenylaminecarbamyl, N,N-dimethylaminecarbamyl, N,N-dibutylaminecarbamyl and N,N-diphenylaminecarbamyl.

As the amine sulfonyl group which may have a substituent, a total of a sulfonyl group having 0 to 30 carbon atoms is preferred. Examples thereof include an amine sulfonyl group, an N-alkylamine sulfonyl group, an N-arylamine sulfonyl group, an N,N-dialkylamine sulfonyl group, an N,N-diarylamine sulfonyl group, and N-alkyl-N-arylamine sulfonyl. Specific examples thereof include N-methylaminesulfonyl, N-ethylaminesulfonyl, N-propylaminesulfonyl, N-butylaminesulfonyl, N-hexylaminesulfonyl, N- Cyclohexylamine sulfonyl, N-octylamine sulfonyl, N-2-ethylhexylamine sulfonyl, N-decylamine sulfonyl, N-octadecylamine sulfonyl, N- Phenylamine sulfonyl, N-2-methylphenylamine sulfonyl, N-2-chlorophenylamine sulfonyl, N-2-methoxyphenylamine sulfonyl, N-2- Isopropoxyphenylamine sulfonyl, N-3-chlorophenylamine sulfonyl, N-3-nitrophenylamine sulfonyl, N-3-cyanophenylamine sulfonyl, N 4-methoxyphenylamine sulfonyl, N-4-cyanophenylamine sulfonyl, N-4-dimethylaminophenylamine sulfonyl, N-4-methylthiophenyl Aminesulfonyl, N-4-phenylthiophenylamine sulfonate , N-methyl-N-phenylamine sulfonyl, N,N-dimethylamine sulfonyl, N,N-dibutylamine sulfonyl and N,N-diphenylamine sulfonate base.

As the amine group which may have a substituent, an amine group having a total of 0 to 50 carbon atoms is preferred. Examples thereof include -NH ₂ , N-alkylamino group, N-arylamino group, N-decylamino group, N-sulfonylamino group, N,N-dialkylamino group, N,N-di Arylamino, N-alkyl-N-arylamine and N,N-disulfonylamino. More specifically, examples thereof include N-methylamino group, N-ethylamino group, N-propylamino group, N-isopropylamino group, N-butylamino group, N-t-butyl group. Amino, N-hexylamino, N-cyclohexylamino, N-octylamino, N-2-ethylhexylamino, N-decylamino, N-octadecylamino, N -benzylamino group, N-phenylamino group, N-2-methylphenylamino group, N-2-chlorophenylamino group, N-2-methoxyphenylamino group, N-2 -Isopropoxyphenylamino, N-2-(2-ethylhexyl)phenylamino, N-3-chlorophenylamino, N-3-nitrophenylamino, N-3 - cyanophenylamino, N-3-trifluoromethylphenylamino, N-4-methoxyphenylamino, N-4-cyanophenylamino, N-4-trifluoro Methylphenylamino, N-4-methylthiophenylamino, N-4-phenylthiophenylamino, N-4-dimethylaminophenylamino, N-methyl- N-phenylamino, N,N-dimethylamino, N,N-diethylamino, N,N-dibutylamino, N,N-diphenylamino, N,N- Diethyl decylamino, N,N-dibenzoylamino, N,N-(dibutylcarbonyl)amine, N,N-(dimethylsulfonyl)amine, N,N- (diethylsulfonyl)amino, N,N-(dibutylsulfonyl)amine , N, N- (diphenyl sulfonic acyl) amino, N- morpholinyl, 3,5-dimethyl-N- morpholino group and a carbazolyl group.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Among them, X in the formula (2) is preferably an alkyl group, an aryl group, an alkenyl group, an alkynyl group, an alkoxy group or an aryloxy group from the viewpoint of increasing solvent solubility and improving absorption efficiency in a long wavelength region. An alkylthio group, an arylthio group or an amine group.

Further, n in the formula (2) represents an integer of 0 to 5, and more preferably an integer of 0 to 2.

Examples of the divalent organic group represented by Y in the formula (2) include the following The structure of the show. Note that in the group shown below, "*" indicates the position of the carbon atom bond adjacent to Y in the formula (2).

Among them, the structure shown below is preferable from the viewpoint of enhancing sensitivity.

The specific hydrazine compound used in the second aspect of the invention is preferably a compound represented by the following formula (3).

In the formula (3), R and X each independently represent a monovalent substituent; A represents a divalent organic group; Ar represents an aryl group; and n represents an integer of 0 to 5.

R, X, A, Ar and n in the formula (3) have the same definitions as R, X, A, Ar and n in the above formula (2), respectively, and preferred examples thereof are also the same.

Specific examples of specific hydrazine compounds used in the second aspect of the invention are shown below, but the invention is not limited thereto.

The specific ruthenium compound used in the second aspect of the present invention preferably has a maximum absorption wavelength in a wavelength region of from 350 nm to 500 nm, and an absorption wavelength in a wavelength region of from 360 nm to 480 nm, and particularly It preferably has an absorption at 365 nm and 455 nm. In particular, a specific ruthenium compound has an absorption in a long wavelength region as compared with a conventional ruthenium-based compound, and thus exhibits excellent sensitivity when exposed by a light source of 365 nm or 405 nm.

From the viewpoint of sensitivity, the specific ruthenium compound used in the second aspect of the present invention preferably has 10,000 to 300,000 moles at 365 nm or 405 nm. The absorption rate, more preferably has a molar absorption of from 15,000 to 300,000, and particularly preferably has a molar absorption of from 20,000 to 200,000. Further, in the present invention, the molar absorption rate of the compound can be measured by using a known method, but in particular, it is preferably by using an ultraviolet-visible spectrophotometer (CARY-5 SPECTROPHOTOMETER (trade name) ), manufactured by Varian Inc., using, for example, an ethyl acetate solvent having a concentration of 0.01 g/liter.

The hexaarylbiimidazole compound used in the second aspect of the present invention has the same definition as the hexaarylbiimidazole compound used in the first aspect of the present invention, and its details (including the preferred range) are also the same.

The content of the (C2) polymerization initiator in the black curable composition according to the second aspect of the present invention is the same as the content of the (C1) polymerization initiator in the black curable composition according to the first aspect of the present invention. And the details (including the preferred range) are also the same.

The black curable composition according to the second aspect of the present invention may contain a chain transfer agent depending on the polymerization initiator to be used. The chain transfer agent used in the second aspect has the same definition as the chain transfer agent used in the first aspect, and the details (including the preferred range) are also the same.

(D2) polymerizable compound

The black curable composition according to the second aspect of the present invention contains a polymerizable compound.

The (D2) polymerizable compound has the same definition as the (D1) polymerizable compound used in the first aspect, and the details (including the preferred range) are also the same.

(E2) Other additives

In the black curable composition according to the second aspect of the present invention, in addition to the components (A2) to (D2) and the pigment dispersant, various additives may be used depending on the purpose.

(E2-1) Binder polymer (alkali soluble resin)

It is preferred to add a binder polymer (for example, a base) to the black curable composition. Soluble resin) for the purpose of improving dispersion stability, developability, film characteristics, and the like. The binder polymer (alkali-soluble resin) may be added during dispersion or may be added during preparation of the curable composition.

Examples of the alkali-soluble resin include a linear organic polymer which is an example of the (E1-1) binder polymer used in the first aspect of the invention.

The alkali-soluble resin preferably further comprises a monomer component (in some cases, hereinafter appropriately referred to as "ether dimer" hereinafter) as a basic component, which is polymerized by a compound having the formula (ED): The polymer (a) formed. By containing the polymer (a), the black curable composition of the present invention can form a cured film having excellent heat resistance and transparency. Hereinafter, in some cases, the compound represented by the formula (ED) may be referred to as "ether dimer".

In the formula (ED), R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.

In the formula (ED), the hydrocarbon group which may have a substituent represented by R ¹ or R ² and has 1 to 25 carbon atoms is not particularly limited. Examples thereof include: a linear or branched alkyl group such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, tert-amyl, stearyl, laurel Or 2-ethylhexyl; aryl, such as phenyl; alicyclic groups, such as cyclohexyl, tert-butylcyclohexyl, dicyclopentadienyl, tricyclodecyl, isobornyl, adamantyl Or 2-methyl-2-adamantyl; alkyl substituted by alkoxy, such as 1-methoxyethyl or 1-ethoxyethyl; and alkyl substituted with aryl, such as phenyl base. Among them, it is particularly preferable to eliminate a primary or secondary hydrocarbon group such as a methyl group, an ethyl group, a cyclohexyl group or a benzyl group by an acid or heat. Further, R ¹ and R ² may be the same or different from each other.

Specific examples of ether dimers include dimethyl 2,2'-[oxybis(methylene)]bis-2-acrylate, 2,2'-[oxybis(methylene)]bis-2 - diethyl acrylate, 2,2'-[oxybis(methylene)]bis-2-n-propyl acrylate, 2,2'-[oxybis(methylene)] double 2-(isopropyl)acrylate, 2,2'-[oxybis(methylene)]bis-2-n-butyl acrylate, 2,2'-[oxybis( Methylene)]bis(isobutyl) bis-2-acrylate, di(tert-butyl) 2,2'-[oxybis(methylene)]bis-2-acrylate, 2,2 '-[oxybis(methylene)]bis(tripentyl) bis-2-acrylate, 2,2'-[oxybis(methylene)]bis-2-propenoic acid di(stearyl) Ester, 2,2'-[oxybis(methylene)]bis-2-laurate, 2,2'-[oxybis(methylene)]bis-2- Di(2-ethylhexyl) acrylate, bis(1-methoxyethyl) 2,2'-[oxybis(methylene)]bis-2-acrylate, 2,2'-[oxygen Bis(methylene)]bis(1-ethoxyethyl) bis-2-acrylate, diphenyl 2,2'-[oxybis(methylene)]bis-2-acrylate, 2,2'-[oxybis(methylene)]di-2-phenyl acrylate, 2,2'-[oxybis(methylene)]bis-2-propene Dicyclohexyl acid ester, bis(t-butylcyclohexyl) 2,2'-[oxybis(methylene)]bis-2-acrylate, 2,2'-[oxybis(methylene) )] bis(dicyclopentadienyl) bis-2-acrylate, bis(tricyclodecyl) 2,2'-[oxybis(methylene)]bis-2-acrylate, 2,2 '-[oxybis(methylene)]bis(isobornyl) bis-2-acrylate, diamantane 2,2'-[oxybis(methylene)]bis-2-propenoate and 2,2'-[oxybis(methylene)]bis(2-methyl-2-adamantyl) bis-2-acrylate. Among them, 2,2'-[oxybis(methylene)]bis-2-acrylic acid dimethyl ester, 2,2'-[oxybis(methylene)]bis-2-propenoic acid diethyl ester, 2,2'-[oxybis(methylene)]dicyclohexyl bis-2-acrylate and 2,2'-[oxybis(methylene)]di-2-methyl acrylate Preferably. The ether dimer may be used singly or in combination of two or more thereof.

The binder polymer preferably contains a polymerizable unsaturated bond. As a method of introducing a polymerizable unsaturated bond, a known method can be used. The unsaturation equivalent of the alkali-soluble resin (the mass of the resin per mole of the unsaturated double bond) is preferably from 400 to 3,000, and most preferably from 500 to 2,000. Within the range, the hardening performance is enhanced, and the adhesion of the light-shielding film to the substrate is improved.

The acid value of the alkali-soluble resin added to the black curable composition according to the second aspect of the present invention is particularly preferably from 10 mgKOH/g to 100 mgKOH/ The gram is more preferably 20 mg KOH/g to 80 mg KOH/g, and most preferably 30 mg KOH/g to 60 mg KOH/g. When the acid value is in the range, the adhesion of the light-shielding film to the substrate and the developability of the unexposed section are satisfied.

The weight average molecular weight of the alkali-soluble resin is preferably from 5,000 to 30,000, and more preferably from 7,000 to 20,000. When the weight average molecular weight is within the above range, the adhesion of the light-shielding film to the substrate and the developability of the unexposed section are satisfied, and the coating characteristics are improved.

The content of the alkali-soluble resin is preferably from 0.1% by mass to 7.0% by mass based on the total solid content of the black curable composition according to the second aspect of the present invention, and the adhesion of the light-shielding film to the ruthenium substrate is improved and From the viewpoint of further improving the inhibition of the development residue, it is more preferably from 0.3% by mass to 6.0% by mass, and still more preferably from 1.0% by mass to 5.0% by mass.

(E2-2) other colorants

The black curable composition according to the second aspect of the present invention may further contain a light-shielding substance other than the inorganic pigment such as a known organic pigment or dye to exhibit desired light-shielding properties.

Examples of the (E2-2) other coloring agent used in combination with the inorganic pigment are the same as those used in the first aspect of the invention as (E1-2) other coloring agents, and the details thereof (including the preferred range) are also the same.

(E2-3) sensitizer

The black curable composition according to the second aspect of the present invention may further contain a sensitizer for the purpose of improving the radical generating efficiency of the polymerization initiator and increasing the wavelength of the photosensitive wavelength.

The sensitizer (E2-3) used in the black curable composition according to the second aspect of the present invention has the same definition as the (E1-3) sensitizer used in the first aspect, and the details thereof ( The best range is included).

(E2-4) polymerization inhibitor

The light-shielding curable composition according to the second aspect of the present invention preferably contains a polymerization inhibitor to inhibit polymerization of the polymerizable compound during preparation or storage of the composition.

The (E2-4) polymerization inhibitor used in the second aspect has the same definition as the (E1-4) polymerization inhibitor used in the first aspect, and the details (including the preferred range) are also the same.

(E2-5) adhesion promoter

An adhesion promoter may be added to the light-blocking hardenable composition according to the second aspect of the present invention to improve the adhesion to the surface of a hard material such as a support.

The example of the (E2-5) adhesion promoter is the same as the example of the (E1-5) adhesion promoter used in the first aspect, and the details (including the preferred range) are also the same.

(E2-6) surfactant

The black curable composition according to the second aspect of the present invention may further comprise any of various surfactants from the viewpoint of further improving coating properties. As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic based surfactant, an anionic based surfactant, or a cerium based surfactant can be used.

In particular, when the black curable composition according to the second aspect of the present invention contains a fluorine-containing surfactant, the liquid properties (especially fluidity) of the composition prepared as the coating liquid are improved, and the thickness of the coating layer is improved. Uniformity and liquid retention characteristics can be improved.

That is, when the black curable composition containing the fluorine-containing surfactant is used to form a film in the form of a coating liquid, the wettability on the surface to be coated is lowered due to the surface tension between the surface to be coated and the coating liquid. It is improved and the coatability on the surface to be coated is improved. Therefore, even when a film having a thickness of several micrometers is formed with a small amount of liquid, a film having a uniform thickness can be suitably formed.

The fluorine content in the fluorine-containing surfactant is preferably from 3% by mass to 40% by mass, more preferably from 5% by mass to 30% by mass, and still more preferably from 7% by mass to 25% by mass. when When the fluorine content of the fluorine-containing surfactant is in the above range, it is effective in terms of uniformity of coating thickness and liquid retention, and excellent solubility can be achieved in the black curable composition.

Examples of the fluorine-containing surfactant include MEGAFAC F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F479, F482, F780, and F781 (trade name, manufactured by DIC Corporation), FLUORAD FC430 , FC431 and FC171 (trade name, manufactured by Sumitomo 3M Limited), SURFLON S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S- 393 and KH-40 (trade name, manufactured by Asahi Glass Co., Ltd.) and SOLSPERSE 20000 (trade name, manufactured by The Lubrizol Corporation).

Examples of the nonionic surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonylphenyl ether, polyethylene Diol dilaurate, polyethylene glycol distearate and sorbitan fatty acid esters such as PLURONIC L10, L31, L61, L62, 10R5, 17R2 and 25R2 and TETRONIC 304, 701, 704, 901, 904 and 150R1 (trade name, manufactured by BASF).

Examples of the cationic surfactant include a phthalocyanine derivative such as EFKA-745 (trade name, manufactured by Morishita & Co., Ltd.); an organic siloxane polymer such as KP341 (trade name, by Shin-Etsu Chemical Co) .Manufactured); (meth)acrylic (co)polymer, such as POLYFLOW 75, 90, 95 (trade name, manufactured by Kyoeisha Chemical Co., Ltd.); and W001 (trade name, available from Yusho Co .,Ltd. obtained).

Examples of the anionic surfactant include W004, W005 and W017 (trade name, available from Yusho Co., Ltd.).

Examples of the polyfluorene surfactant include TORAY SILICONE DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, and SH8400 (trade name, manufactured by Dow Corning Toray Co., Ltd.), TSF-4440, 4300, 4445, 444(4)(5)(6)(7)6, 4460 and 4452 (trade name, by Momentive Manufactured by Performance Materials Inc., KP341 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), and BYK 323 and 330 (trade name, manufactured by BYK Chemie).

The surfactant may be used singly or in combination of two or more kinds of surfactants.

The black curable composition according to the second aspect of the present invention can be obtained by using (A2) inorganic pigment, (B2) specific resin, (C2) polymerization initiator, (D2) polymerizable compound, and optionally Various additives are added to the solvent and further prepared by mixing with an optional additive such as a surfactant.

The above black curable composition according to the second aspect of the present invention is provided on the back surface of the ruthenium substrate having the photographic element section on the front surface, and can be used (not particularly limited) for blocking the infrared light. (i.e., in a light-blocking film for blocking infrared light incident on the back side of a substrate (which has a solid-state imaging element)).

Also, in the solid-state imaging element, the structure of the solid-state imaging element according to the second aspect described below strongly requires blocking of infrared light incident from the back side and it is necessary to reduce development residue on the metal electrode. For the reason described, the second black curable composition of the present invention having an infrared light-improving effect and reducing the effect of the residue is particularly suitable for forming a light-shielding film of the solid-state photographic element according to the second aspect described below.

Black curable composition according to the third aspect

Hereinafter, the black curable composition according to the third aspect of the present invention will be described in detail.

The black curable composition according to the third aspect of the present invention comprises (A3) an inorganic pigment, (B3) a chain resin comprising a solvent-compatible portion and a pigment-adsorbing moiety having an acid group or a base (hereinafter appropriate It is called "specific resin", (C3) polymerization initiator, and (D3) polymerizable compound. Hereinafter, each component contained in the black curable composition according to the third aspect of the present invention will be described in order.

(A3) inorganic pigment

As a black curable composition according to the third aspect of the present invention The (A3) inorganic pigment contains a pigment having an absorption effect at a wavelength in the range of ultraviolet light to infrared light from the viewpoint of exhibiting light-shielding properties in a region from visible light to infrared light.

Specific examples of the (A3) inorganic pigment used in the third aspect of the present invention are the same as the specific examples of the (A1) inorganic pigment used in the first aspect, and the details (including the preferred range) are also the same.

In the third aspect, only one inorganic pigment may be used, or a mixture of a plurality of inorganic pigments may be used to achieve the purpose of exhibiting light-shielding properties for a wide wavelength region in the visible to infrared range.

As the (A3) inorganic pigment used in the third aspect, a metallic pigment or titanium black containing silver or tin is preferable from the viewpoint of light shielding properties and hardening properties, and titanium black is for visible light to infrared light. It is optimal from the viewpoint of the light-shielding property of the wavelength region.

The titanium black used in the third aspect has the same definition as the titanium black used in the first aspect, and the details (including the preferred range) are also the same.

The method of producing the titanium black used in the third aspect is the same as the method of producing the titanium black used in the first aspect.

The average primary particle diameter of the titanium black particles used in the third aspect has the same definition as the average primary particle diameter of the titanium black particles used in the first aspect, and the details (including the preferred range) are also the same.

The (A3) inorganic pigment (such as titanium black) according to the third aspect of the present invention preferably has an average particle diameter of from 5 nm to 500 nm, and is in view of dispersibility, light-shielding property, and precipitation over time. The average particle diameter is preferably from 10 nm to 100 nm.

In the black curable composition according to the third aspect of the invention, the inorganic pigment (A3) may be used singly or in combination of two or more kinds of inorganic pigments. Further, as described below, in order to achieve the purpose of adjusting the light-shielding property or other purposes, an organic pigment, a dye or the like may be used in combination with the inorganic pigment as necessary.

In the black hardening composition (A3) inorganic pigment content to constitute The total mass of the substance is preferably from 5% by mass to 70% by mass, and more preferably from 10% by mass to 50% by mass. When the content is in the above range, excellent light-shielding properties and developability at the time of pattern formation are achieved.

When the (A3) inorganic pigment is incorporated into the black curable composition, the (A1) inorganic pigment is preferably blended in the form of a pigment dispersion in terms of the uniformity of the obtained composition, wherein the inorganic pigment ( B3) has been previously dispersed by a specific resin or the like.

(B3) a chain resin comprising a solvent-compatible portion and a pigment-adsorbing moiety having an acid group or a base

The black curable composition according to the third aspect of the present invention comprises (B3) a chain resin comprising a solvent-compatible portion and a pigment-adsorbing moiety having an acid group or a base (hereinafter, appropriately referred to as "(B3) )Specific resin").

(B3) The specific resin is a chain resin containing a solvent-compatible portion and a pigment-adsorbing portion having an acid group or a base (hereinafter referred to as "pigment-adsorbing portion" as appropriate) as a constituent unit.

The adhesion of the black curable composition according to the third aspect of the present invention to the substrate is improved by containing a specific resin. In particular, in applications for wafer level lenses, adhesion to the lens and adhesion to the glass substrate, which are difficult to achieve simultaneously, are achieved. Also, in order to form an infrared-shielding film provided on one surface of the ruthenium substrate (the ruthenium substrate has a solid-state photographic element on the other surface), when the black curable composition according to the third aspect of the present invention is used It is difficult to achieve the adhesion of the solder resist layer and the adhesion to the metal electrode.

(B3) The solvent-compatible portion contained in the specific resin contains a constituent unit exhibiting solvent compatibility. The solvent compatibility as used herein means high solubility in propylene glycol monomethyl ether acetate which is a main component of the solvent contained in the black hardenable composition. To exhibit solvent compatibility, the (B3) specific resin preferably comprises repeating units having an I/O value close to the I/O value (0.67) of propylene glycol monomethyl ether acetate.

The I/O value of the repeat unit is close to the I/O value of propylene glycol monomethyl ether acetate (0.67) means an I/O value of 0.05 to 1.50, preferably 0.03 to 1.30, and more preferably 0.40 to 0.70. When (B3) the specific resin contains a repeating unit having an I/O value within the range, the dispersion stability is further improved. It is believed that this is because the specific resin is used when the I/O value of the specific resin is close to 0.67 (the I/O value of propylene glycol monomethyl ether acetate which is the main component of the solvent used in the black hardenable composition). The compatibility is enhanced to inhibit pigment aggregation.

From the viewpoint of dispersion stability, the (B3) specific resin preferably contains 80% by mass or more, more preferably 90% by mass or more, and most preferably 95% by mass, and I/O value in the solvent compatibility portion. The unit is a solvent compatible repeat of 0.05 to 1.50.

In the third aspect of the present invention, the content of the constituent unit exhibiting solvent compatibility contained in the specific resin is preferably from 30% by mass to 95% by mass in terms of solubility and dispersion stability, and More preferably, it is 40% by mass to 95% by mass, and most preferably 50% by mass to 90% by mass.

The I/O value is a value for treating the polarity of various organic compounds, and is also called (inorganic value) / (organic value) in terms of organic concept, and is used in a functional group contribution method for setting a functional group parameter. Details of the I/O values are disclosed in documents such as ORGANIC CONCEPTUAL DIAGRAMS (by KODA Yoshi, published by Sankyo Publishing Co., Ltd. (1984)), KUMAMOTO PHARMACEUTICAL BULLETIN, No. 1, lines 1 to 16 ( 1954); Chemical Field, Vol. 11, No. 10, pp. 719-725 (1957); FRAGRANCE JOURNAL, No. 34, pp. 97-111 (1979); FRAGRANCE JOURNAL, No. 50, pp. 79-82 Line (1981); and similar documents.

The concept of I/O value should be such that the properties of the compound can be divided into organic groups exhibiting covalent bond characteristics and inorganic groups exhibiting ionic bond characteristics, and each organic compound can be named as the axis of the vertical axis of the organic axis and the inorganic axis. One point is for evaluation.

The inorganic value refers to the magnitude of the influence of various substituents or bonds contained in the organic compound on the boiling point, and is represented numerically using a hydroxyl group as a reference. In particular, since the boiling point curve of a linear alcohol and the boiling point of a linear paraffin are obtained at about 5 carbon atoms The distance between the curves (equal to 100 ° C) specifies the effect of a hydroxyl group as a value of 100, and based on this value, the value indicating the influence of various substituents or bonds on the boiling point is the substituent contained in the organic compound. Inorganic value. For example, the -COOH group has an inorganic value of 150 and the double bond has an inorganic value of 2. Therefore, the inorganic value of an organic compound means the sum of the inorganic values of various substituents, bonds and the like contained in the organic compound.

The organic value is determined by using the influence of the carbon atom represented by a methylene group (which is designated as a unit in the molecule) on the boiling point as a reference. In other words, since the boiling point is increased by 20 ° C due to the addition of one carbon atom to the linear saturated hydrocarbon compound having about 5 to 10 carbon atoms, based on this, the organic value of one carbon atom is designated as 20, Based on this, the numerical value indicating the influence of various substituents or bonds on the boiling point is an organic value. For example, the organic value of nitro (-NO ₂ ) is 70.

The I/O value indicates an organic compound that is non-polar (hydrophobic and has substantial organic properties) when it is close to 0, and an organic compound that is polar (hydrophilic and has substantial inorganic properties) when it is large.

In the following, a method of calculating the I/O value is described.

The I/O value of the repeating unit (A) shown below can be calculated by using the method described below to calculate the organic value and the inorganic value of the repeating unit, and then according to the following formula (inorganic value of the copolymer) / (copolymer) Organic value) is calculated to obtain.

The repeating unit (A) has an ester group, and thus the inorganic value of the repeating unit (A) is calculated as follows: 60 (inorganic value of the ester group) × 1 (number of ester groups) = 60.

The repeating unit (A) has 8 carbon atoms, and thus the organic value of the repeating unit (A) is calculated as follows: 20 (organic value of carbon atoms) × 8 = 160.

Therefore, the I/O value of the copolymer was as follows: 60 (inorganic value of copolymer) / 160 (organic value of copolymer) = 0.38.

Specifically, the repeating unit forming the solvent-compatible portion is preferably a repeating unit represented by the following formula (I-A) or the following formula (I-B).

In the formula (IA), R ¹ represents an alkoxy group, a cycloalkoxy group or an aryloxy group. The alkoxy group represented by R ¹ is preferably a chain or cyclic alkoxy group having 1 to 30 carbon atoms, and more preferably a chain or cyclic alkoxy group having 1 to 10 carbon atoms, and A part of the carbon atom of the alkoxy group may be substituted with a hetero atom such as an oxygen atom, a nitrogen atom or a sulfur atom. Specific examples thereof include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a second butoxy group, a third butoxy group, a pentyloxy group, an isopentyloxy group, and a third pentoxide. , neopentyloxy, hexyloxy, 2-ethylhexyloxy, octyloxy, decyloxy, dodecyloxy, 2-methoxyethyl, 3-ethoxyethyl, 2 -(2-methoxyethoxy)ethyl, benzyloxy, 2-hydroxyethoxy and 3-hydroxypropoxy.

The cycloalkyl group represented by R ¹ is preferably a monocyclic or polycyclic cycloalkyl group having 3 to 30 carbon atoms, and most preferably a monocyclic or polycyclic cycloalkyl group having 5 to 20 carbon atoms, and A part of the carbon atom of the cycloalkoxy group may be substituted with a hetero atom such as an oxygen atom, a nitrogen atom or a sulfur atom. Specific examples thereof include cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, cyclooctyloxy, cyclodecyloxy, bicyclo[1,2,2]hept-2-yloxy, Bicyclo[2,2,2]oct-3-yloxy and tricyclo[5.2.1.0 ^2.6 ]癸-8-yloxy.

The aryloxy group represented by R ¹ is preferably an aryloxy group having 6 to 30 carbon atoms, and more preferably an aryloxy group having 6 to 20 carbon atoms. Examples of the aryloxy group preferably include a phenoxy group, a 1-naphthyloxy group, and a 2-naphthyloxy group. R ^{1 is} particularly preferably an alkoxy group having 1 to 10 carbon atoms or a cycloalkoxy group having 5 to 15 carbon atoms.

R ² represents a hydrogen atom, a halogen atom or an alkyl group. The alkyl group represented by R ² is preferably an alkyl group having 1 to 5 carbon atoms, and more preferably a methyl group, a 2-hydroxymethyl group or a trifluoromethyl group from the viewpoint of polymerization characteristics. R ^{2 is} particularly preferably a hydrogen atom or a methyl group.

In the formula (IB), R ³ represents an aryl group; and R ⁴ represents a hydrogen atom or an alkyl group.

The aryl group represented by R ³ is preferably an aryl group having 6 to 30 carbon atoms, more preferably an aryl group having 6 to 20 carbon atoms, and most preferably an aryl group having 6 to 15 carbon atoms. Specific examples thereof include a phenyl group and a naphthyl group.

Hereinafter, specific examples of the formula (IA) and the formula (IB) are shown, but the invention is not limited thereto. Also, in certain instances, R ² in the formula (IA) R ² have the same definitions of R ⁴ and R in the formula (IB) ⁴ having the same definitions.

From the viewpoint of dispersion stability, in the repeating unit, a repeating unit represented by (IA-1) to (IA-17) and (IA-23) and having (meth) acrylate as a monomer (wherein R ² is a hydrogen atom or a methyl group) and a repeating unit represented by (IB-1) and having styrene as a monomer (wherein R ⁴ is a hydrogen atom) is preferred.

The solvent compatible moiety may comprise two or more repeating units that exhibit solvent compatibility.

The solvent-compatible portion may further comprise, as a repeating unit, a repeating unit having an I/O value not in the range of 0.05 to 1.50, in addition to the repeating unit exhibiting solvent compatibility. Examples of the repeating unit other than the repeating unit exhibiting solvent compatibility include a repeating unit having a polar group such as an acid group, a hydroxyl group or a decyl group, and a repeating unit composed only of an alkyl group or an alkenyl group.

The repeating unit other than the repeating unit exhibiting solvent compatibility has an I/O value of less than 0.05, or more than 1.50, and preferably equal to or less than 0.03, or equal to or greater than 2.00.

Specific examples of the repeating unit other than the repeating unit exhibiting solvent compatibility include a repeating unit containing methacrylic acid (I/O value: 4.375), a repeating unit containing acrylic acid (I/O value: 5.833), and a methyl group. a repeating unit of 2-hydroxyethyl acrylate (I/O value: 1.33), a repeating unit comprising 2,3-dihydroxypropyl methacrylate (I/O value: 1.857), containing N-vinylpyrrolidone Repeating unit (I/O value of 2.1), repeating unit containing N,N-dimethylpropenylamine (I/O value: 0.875), repeating unit containing ethylene (I/O value of 0), and inclusion Repeat unit of isoprene (I/O value is 0.02). The content of the repeating unit is 20% by mass or less based on the total mass, and preferably 10% by mass or less.

When the solvent-compatible portion has an acid group, the acid value (mole of the acid group contained in the solvent-compatible portion (mole) × 56.1 (g-KOH/mole) / solvent compatibility The mass (m) of the part is 20 mgKOH/g or less, and preferably 10 mgKOH/g. When the acid value is larger than this value, the dispersion stability is lowered.

From the viewpoint of dispersion stability, the weight average molecular weight of the solvent-compatible portion according to the GPC measurement is preferably in the range of 2,000 to 30,000, more preferably in the range of 3,000 to 20,000, and most preferably in the range of 5,000 to 15,000. Within the scope. Herein, when the resin is introduced into the solvent-compatible portion, the weight average molecular weight is Mw1. When the weight average molecular weight of the resin after introduction of the solvent-compatible portion is represented by Mw2, the "weight average molecular weight of the solvent-compatible portion" is defined as "Mw2-Mw1".

A pigment-adsorbing moiety having an acid group or a base in a specific resin is described. The "pigment-adsorbing moiety having an acid group or a base" as described herein preferably comprises a monomer having at least one of an acid group and a base and having a molecular weight in the range of 70 to 500 (hereinafter, also referred to as A repeating unit of "acid-containing monomer" or "base-containing monomer".

The acid group-containing monomer is preferably a (meth)acrylic substrate and a styrene substrate from the viewpoint of polymerization. Examples of the acid group contained in the acid group-containing monomer include a carboxylic acid, a phosphoric acid, and a sulfonic acid.

The specific structure including the repeating unit of the acid group-containing monomer is shown below, but the invention is not limited thereto. R _A in the following formula represents a hydrogen atom, a methyl group, a hydroxymethyl group or a trifluoromethyl group.

Among the repeating units containing an acid group-containing monomer, (B-1) and (B-4) to (B-12) which are repeating units containing a carboxyl group are particularly preferable from the viewpoint of dispersion stability.

The repeating unit comprising a base-containing monomer refers to a repeating unit comprising a monomer having at least one base and having a molecular weight in the range of 70 to 500 (hereinafter, also referred to as "base-containing monomer"). The base-containing monomer is preferably a (meth)acryl base and a styrene base from the viewpoint of dispersion stability. As the base contained in the base-containing monomer, an amine group and a nitrogen-containing heterocyclic group are preferred, an amine group and a pyridyl group are more preferable, and an amine group is most preferable.

The specific structure including the repeating unit of the base-containing monomer is shown below, but the invention is not limited thereto. R _B in the following formula represents a hydrogen atom, a methyl group, a hydroxymethyl group or a trifluoromethyl group.

Among the repeating units containing a base, specifically, (B-14) to (B-31) and (B-34) to (B-36) having an amine group are preferred from the viewpoint of dispersion stability. (B-14) to (B-31) having a tertiary amino group, and (B-14) to (B-19) And (B-22) and (B-25) are the best.

When the specific resin contains a repeating unit containing an acid group, the acid value is preferably from 50 mgKOH/g to 150 mgKOH/g, more preferably from 60 mgKOH/130 g to 130 mgKOH/g, and most preferably 75 mg. KOH / g to 120 mg KOH / g. When the acid group is in the above range, the adhesion to the glass substrate and the lens is satisfied.

When the specific resin contains a base, the amine value is preferably from 50 mgKOH/g to 150 mgKOH/g, more preferably from 60 mgKOH/g to 140 mgKOH/g, and most preferably from 75 mgKOH/g to 120 mg KOH / g. When the amine value is within the above range, the adhesion to the glass substrate and the lens is satisfied. From the viewpoint of developability, the pigment adsorbing moiety in the specific resin is preferably composed of repeating units including, in particular, an acid group.

From the viewpoint of adhesion, the weight average molecular weight of the pigment-adsorbing portion in the specific resin according to the GPC measurement method is preferably in the range of 500 to 10,000, more preferably in the range of 1,000 to 5,000, and most preferably in the range of 1,000 to 10,000. Within 3,000. Herein, when the weight average molecular weight of the resin before introduction into the pigment adsorbing moiety is represented by Mw1, and the weight average molecular weight of the resin after introduction of the pigment adsorbing moiety is represented by Mw2, the definition of "weight average molecular weight of the pigment adsorbing moiety" It is "Mw1-Mw2".

The pigment-adsorbing moiety may comprise two or more repeating units having an acid group and a base.

The pigment-adsorbing moiety having an acid group or a base may include a repeating unit other than a repeating unit containing an acid group or a base, and examples of the repeating unit include an alkyl group, an alkylene oxide, a cyano group, a decylamino group, A hydroxyl group, a lactone group, an aromatic ring group, and a heterocyclic group.

Specific examples of the repeating unit other than the repeating unit containing an acid group or a base include a repeating unit represented by (IA-1) to (IA-24), (IB-1), and (IB-2); a repeating unit; a repeating unit comprising N,N-dimethylpropenylamine; and a repeating unit comprising N-vinylpyrrolidone and 2-hydroxyethyl methacrylate. The content of the repeating unit is 10% by mass or less based on the total mass of the pigment adsorbing portion, but It is preferably 5% by mass.

The pigment-adsorbing moiety having an acid group or a base preferably contains an amount of 90% by mass or more, more preferably 95% by mass, and most preferably 99% by mass of a repeating unit containing an acid group or a base. When the content is within the range, the adhesion is further improved.

The content of the solvent-compatible portion and the pigment-adsorbing portion (in terms of mass ratio) in a specific resin (that is, the solvent-compatible portion: pigment-adsorbing portion) is preferably 95:5 to 30:70, more preferably It is from 90:10 to 40:60, and most preferably from 90:10 to 50:50. When the mass ratio is within the range, the dispersion stability and adhesion are further improved.

The weight average molecular weight of the specific resin is preferably in the range of 5,000 to 25,000, more preferably in the range of 6,000 to 20,000, and most preferably in the range of 7,000 to 15,000, according to GPC measurement. When the weight average molecular weight is within the range, the dispersion stability is remarkably improved.

The specific resin in the present invention is a chain-like dispersing resin intentionally incorporating a solvent-compatible portion and a pigment-adsorbing portion. The method of introducing the solvent-compatible portion and the pigment-adsorbing portion is preferably a living polymerization method, and particularly preferably a living radical polymerization method. The living radical polymerization method is preferably a living radical polymerization method which is carried out in the presence of a nitroxide radical as disclosed in Japanese Patent No. 4,304,014 or in the presence of a dithioester as disclosed in JP-A No. 2009-9114. The living radical polymerization method is carried out.

Structure of a specific resin containing a solvent compatible portion and a pigment adsorbing portion

Solvent compatibility is achieved when the solvent compatible moiety consists of only one repeating unit exhibiting solvent compatibility and the pigment adsorbing moiety consists solely of repeating units comprising an acid group-containing monomer or a base-containing monomer Part of the monomer P is polymerized with the monomer Q constituting the pigment adsorbing moiety. In this case, in the method of performing polymerization by mixing with a radical generator in a state where P and Q are mixed, the repeating unit containing P and Q is substantially randomly arranged as follows.

PPPQPPQP...PPQPQPPQPPQP

(randomly arranged part)

In contrast, in the case of the specific resin used in the third aspect of the present invention, since a single repeating unit (or the same repeating unit) is polymerized, the specific resin obtained has a plurality of portions in which P or Q are continuously arranged. In this case, the specific resin is a block polymer.

In particular, the specific resin may have a PQ-type structure including one structural unit formed of a plurality of Ps and one structural unit formed of a plurality of Qs, or may have two structural units each composed of a plurality of Ps and one A PQP type structure of a structural unit formed of a plurality of Qs. Specifically, the specific resin preferably has a PQ type structure from the viewpoint of adhesion characteristics.

The presence of a solvent-compatible portion and a pigment-adsorbing portion (PQ type)

‧PPPPPPPPPPPPPPP-QQQQQQQQQQQQ

(solvent compatible part) - (pigment adsorption part)

The presence of a solvent-compatible portion, a pigment-adsorbing portion, and a solvent-compatible portion (PQP type)

‧PPPPPPPPPPPP-QQQQQQQQQQ-PPPPPPPPPPPPP

(solvent compatible part) - (pigment adsorbing moiety) - (solvent compatible part)

When the solvent-compatible portion contains the repeating unit A other than the repeating unit P exhibiting solvent compatibility and the pigment adsorbing property includes the repeating unit B other than the repeating unit Q formed of the acid group-containing monomer or the base-containing monomer The situation similar to the PQ type is as follows.

‧PPPPAPPPPAAA-BQQQQQQBBQQQQQ

Here, when A and B have the same structure, the structure of the specific resin is as follows. In the following structure, the solvent-compatible group indicates a portion other than the constituent elements of the constituent element which form the pigment-adsorbing moiety having an acid group or a base.

‧PPPPAPPPPAAA-AQQQQQQAAQQQQQ

In the present invention, in the above-described situation, the portion "QQQQQQQQQQQQQ" in which AA is inserted into a plurality of Qs is defined as a pigment adsorbing portion, and a portion other than the pigment adsorbing portion except "PPPPAPPPPAAA-A" is defined as a solvent. compatibility section. Similarly, in the case where there are two or more kinds of repeating units exhibiting solvent compatibility in the structure and/or two or more kinds of repeating units formed of an acid group-containing monomer or a base group-containing monomer, A portion of the repeating unit in which the base monomer or the base-containing monomer is formed is defined as a pigment-adsorbing moiety, and the remainder is defined as a solvent-compatible moiety. The amount of "A" contained in the pigment adsorbing portion is 10% by mass or less, and preferably 5% by mass or less based on the total mass of the pigment adsorbing portion.

When the hardenable composition according to the third aspect of the present invention is prepared, the specific resin may be added in a solid form or may be added after being dissolved in a solvent. In the case where the specific resin is dissolved in the solvent, the specific resin is preferably dissolved in the (F3) organic solvent described below. The solution of the specific resin can be prepared by dissolving a solid specific resin in a solvent, or by dissolving a monomer constituting a specific resin in a solvent and then polymerizing it. When a specific resin is used in the form of a solution obtained by dissolving a specific resin in a solvent, the concentration of the solid content in the solution is preferably from 10% by mass to 70% by mass, and preferably from 20% by mass to 50% by mass. %.

In the black curable composition, the content of the specific resin is preferably in the range of 2% by mass to 30% by mass, and more preferably in the range of 5% by mass to 20% by mass, based on the solid content of the black curable composition. Inside.

The black curable composition according to the third aspect of the present invention can be previously prepared as a pigment dispersion liquid by adding an inorganic pigment to a specific resin and other pigment dispersants in a specific resin. As other pigment dispersants, well-known pigment dispersants and surfactants can be appropriately selected and used.

Examples of other pigment dispersants which can be used in the third aspect are the same as those of the dispersant used in combination with the (B1) specific resin used in the first aspect, and the details (including the preferred range) are also the same.

The resin having a polyester chain in the side chain disclosed in the specification of JP-A No. 2010-106268 filed by the applicant of the present application is preferred from the viewpoints of dispersibility, developability and precipitation characteristics. a resin having a polyester chain in a side chain, especially From the viewpoint of dispersibility, it is preferable that the resin having an acid group is more preferable from the viewpoint of dispersibility and resolution. As a preferred acid group, an acid group having a pKa of 6 or less is preferable from the viewpoint of adsorption characteristics, and specifically, a carboxylic acid, a sulfonic acid, and an acid group derived from phosphoric acid are preferable.

From the viewpoint of solubility, dispersibility, and developability in the pigment dispersion liquid, a resin having a polyester chain and having a carboxylic acid group on the polycaprolactone chain is preferred.

In the preparation of the pigment dispersion, the content of the other pigment dispersant is preferably from 1% by mass to 90% by mass, and more preferably from 3% by mass to 70% by mass. When the content is within the range, the substrate adhesion property is better.

(C3) polymerization initiator

The black curable composition according to the third aspect of the present invention contains (B3) a polymerization initiator.

The (C3) polymerization initiator used in the black curable composition of the third aspect of the invention has the same definition as the (C1) polymerization initiator used in the black curable composition of the first aspect, and The details (including the preferred range) are also the same.

In the third aspect of the present invention, among the oxime ester-based compounds, the compound represented by the following formula (a) is preferred from the viewpoints of sensitivity, stability with time, and coloring during post-heating. of. IRGACURE OXE-01, OXE-02 manufactured by Ciba Specialty Chemicals is preferred.

In the formula (a), R and X each independently represent a monovalent substituent; A represents a divalent organic group; and Ar represents an aryl group; and n represents an integer of 1 to 5.

R is preferably a sulfhydryl group from the viewpoint of enhancing sensitivity, and in particular, Preferred is an ethyl hydrazide group, a propyl fluorenyl group, a benzamidine group or a tolylmethyl group.

A is preferably an unsubstituted alkylene group for the purpose of enhancing sensitivity and inhibiting coloring due to heat aging; and alkyl group (e.g., methyl, ethyl, tert-butyl or dodecyl) a substituted alkyl group; an alkyl group substituted with an alkenyl group (e.g., a vinyl group or an allyl group); or an aryl group (e.g., phenyl, p-tolyl, xylyl, cumyl, naphthyl, Alkyl, phenanthryl or styryl) substituted alkyl.

Ar is preferably a substituted or unsubstituted phenyl group from the viewpoint of enhancing sensitivity and suppressing coloring due to heat aging. In the case of a substituted phenyl group, examples of the substituent thereof include a halogen group such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

From the viewpoints of solubility and improvement of the absorption efficiency in the long-wavelength region, X is preferably an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkenyl group which may have a substituent, an alkyne which may have a substituent A group, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylthio group which may have a substituent, an arylthiooxy group which may have a substituent, and an amine group.

In the formula (a), n preferably represents 1 or 2.

In the following, specific examples (3-1-1) to (3-1-23) of the oxime ester compound are shown.

The hexaarylbiimidazole compound used in the third aspect of the present invention has the same definition as the hexaarylbiimidazole compound used in the first aspect of the present invention, and the details thereof (including the preferred range) are also the same.

The content of the (C3) polymerization initiator in the black curable composition according to the third aspect of the present invention is the same as the content of the (C1) polymerization initiator in the black curable composition according to the first aspect of the present invention. And the details (including the preferred range) are also the same.

Depending on the polymerization initiator used, the black aspect according to the third aspect of the present invention The color hardening composition may comprise a chain transfer agent. The chain transfer agent used in the third aspect has the same definition as the chain transfer agent used in the first aspect, and the details (including the preferred range) are also the same.

(D3) polymerizable compound

The black curable composition according to the third aspect of the present invention contains a polymerizable compound.

The (D3) polymerizable compound used in the third aspect has the same definition as the (D1) polymerizable compound used in the first aspect, and the details (including the preferred range) are also the same.

The polymerizable compound used in the third aspect may be used singly or in combination of two or more kinds thereof. For example, as a combination example, in terms of developability/adhesion, it is preferred to use a combination of two monomers having different polymerizable groups, and it is more preferable to use a polymerizable group having four or less. A combination of a monomer (i.e., a tetrafunctional or lower functionality monomer) with a monomer having five or more polymerizable groups (i.e., a pentafunctional or higher functionality monomer).

The content of the polymerizable compound in the black curable composition is preferably from 3 parts by mass to 55 parts by mass, and more preferably from 10 parts by mass to 50 parts by mass, per 100 parts by mass of the total solid content. When the content of the polymerizable compound is within the above range, the hardening reaction proceeds sufficiently.

(E3) Other additives

In the black curable composition according to the third aspect of the present invention, in addition to the components (A3) to (D3) and other pigment dispersants, various additives may be used depending on the purpose.

(E3-1) Binder polymer (alkali soluble resin)

The black curable composition according to the third aspect of the present invention may contain (E3-1) alkali-soluble resin (hereinafter, simply referred to as "alkali-soluble resin") different from the resin having the component (B3).

The alkali-soluble resin which can be used in the third aspect of the present invention can be suitably selected from the group consisting of alkali-soluble resins which are linear organic high molecular polymers and a group having at least one alkali solubility promoting a molecule thereof (preferably a molecule containing an acrylic copolymer or a styrene copolymer in the main chain) (for example, a carboxyl group, a phosphoric acid group, a sulfonic acid group, a hydroxyl group or the like) group).

The alkali-soluble resin is more preferably an acrylic copolymer or the like, such as a polymer having a carboxylic acid in a side chain, such as a methacrylic acid copolymer, an acrylic copolymer, an itaconic acid copolymer, a butenoic acid copolymer, Maleic acid copolymer, partially esterified maleic acid copolymer and the like (for example, JP-A No. 59-44615, JP-B No. 54-34327, JP-B No. 58-12577 , JP-B No. 54-25957, JP-A No. 59-53836, JP-A No. 59-71048); an acidic cellulose derivative having a carboxylic acid in a side chain; The one obtained by adding to a polymer having a hydroxyl group.

The acid value of the alkali-soluble resin is preferably from 20 mgKOH/g to 200 mgKOH/g, more preferably from 30 mgKOH/150 to 150 mgKOH/g, and most preferably from 50 mgKOH/kg to 120 mgKOH/ Gram.

Specific examples of the alkali-soluble resin include a copolymer of (meth)acrylic acid and other monomers copolymerizable therewith. Examples of other monomers copolymerizable with (meth)acrylic acid include alkyl (meth)acrylate, aryl (meth)acrylate, vinyl compounds, and the like. Here, the hydrogen atom of the alkyl group and the aryl group may have a substituent.

The alkyl (meth)acrylate and the aryl (meth)acrylate comprise CH ₂ =C(R ¹¹ )(COOR ¹³ ) (wherein R ¹¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ¹³ represents An alkyl group having 1 to 8 carbon atoms or an aralkyl group having 6 to 12 carbon atoms), especially comprising methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, Butyl (meth)acrylate, isobutyl (meth)acrylate, amyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, phenyl (meth)acrylate, ( Methyl methacrylate, cresyl (meth) acrylate, naphthyl (meth) acrylate, cyclohexyl (meth) acrylate, hydroxyalkyl (meth) acrylate (alkyl group has 1 to 8 An alkyl group of a carbon atom, a methacrylate hydroxy glycidyl ester, tetrahydrofuran methyl methacrylate, and the like.

An alkali-soluble resin having a polyoxyalkylene chain in the side chain is preferred. Polyoxyalkylene The chain comprises a polyoxyethylene chain, a polyoxypropylene chain, a polybutylene glycol chain, or a combination thereof.

The number of repeating units of the polyoxyethylene chain and the polyoxypropylene chain is preferably from 1 to 20, and more preferably from 2 to 12. Preferred examples of the acrylic copolymer having a polyoxyalkylene chain in a side chain as a copolymerization component include 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, and polyethylene glycol mono( Methyl) acrylate, polypropylene glycol mono (meth) acrylate, poly(ethylene glycol-propylene glycol) mono (meth) acrylate and the like, and compounds in which the alkyl group is terminated by a terminal OH group, for example Methoxy polyethylene glycol mono(meth)acrylate, ethoxypolypropylene glycol mono(meth)acrylate, methoxy poly(ethylene glycol-propylene glycol) mono(meth)acrylate and the like .

Vinyl compound CH ₂ =CR ¹² R ¹⁴ (wherein R ¹² represents an aromatic hydrocarbon ring having 6 to 10 carbon atoms, R ¹⁴ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms), particularly styrene , α-methylstyrene, vinyl toluene, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, polystyrene macromonomer, polymethyl methacrylate macromonomer, and the like.

Other copolymerizable monomers may be used singly or in combination of two or more kinds thereof. Other preferred copolymerizable monomers include alkyl (meth)acrylate (alkyl represents an alkyl group having 2 to 4 carbon atoms), phenyl (meth)acrylate, benzyl (meth)acrylate, and styrene. .

Examples of the alkali-soluble resin used in the third aspect include the ether dimer represented by the formula (ED) which can be used in the second aspect, and the definitions and details (including the preferred range) are also the same.

Among the vinyl compounds, a benzyl (meth)acrylate/(meth)acrylic copolymer or a multicomponent copolymer composed of benzyl (meth)acrylate/(meth)acrylic acid/other monomer Especially preferred.

The acid value of the acrylic resin is in the range of 20 mgKOH/kg to 200 mgKOH/g as described above. When the acid value is in the range, the solubility of the base to the acrylic resin becomes suitable, and thus it is possible to broaden the optimum range of development. Surround (development latitude).

The weight average molecular weight Mw of the acrylic resin (corresponding value of polystyrene measured by the GPC method) is preferably from 2,000 to 100,000, and more preferably from 3,000 to 50,000, to achieve ease in the process (such as black hardening composition). The range of viscosity used during the application and the strength of the film.

The amount of addition of the alkali-soluble resin to the black curable composition of the present invention is preferably from 5% by mass to 70% by mass, and more preferably from 10% by mass to 60% by total solid content of the black curable composition. quality%. When the equivalent is in the range, the film strength is appropriately improved and the solubility during development is easily controlled. This is preferred because a coated film having the desired thickness is achieved.

Further, in order to improve the crosslinking efficiency of the black curable composition of the present invention, an alkali-soluble resin having a polymerizable double bond in a side chain of the polymer is preferably used. Specifically, an alkali-soluble resin containing a (meth)acryl fluorenyl group in a side chain is preferably used. Thereby, the sensitivity is improved and the residue on the lens or the glass substrate is further reduced.

Examples of the polymer containing a polymerizable double bond are shown below, but are not limited to the following examples as long as an alkali-soluble group such as a COOH group or an OH group and an unsaturated bond between carbon atoms are contained.

A urethane-modified acrylic resin containing a polymerizable double bond obtained by reacting a compound containing at least one (meth) acrylonitrile group with an acrylic resin containing a carboxyl group, which is derived from an isocyanate The group is obtained by reacting with an OH group to exclude an unreacted isocyanate group.

An unsaturated group-containing acrylic resin obtained by reacting a carboxyl group-containing acrylic resin with a compound having an epoxy group and a polymerizable double bond in a molecule.

Acid side-position epoxy acrylate resin.

An acrylic resin containing a polymerizable double bond obtained by reacting an acrylic resin containing an OH group with a dibasic acid anhydride having a polymerizable double bond.

Among them, the resins of (1) and (2) are particularly preferred.

The alkali-soluble resin having a polymerizable double bond in the present invention preferably has an acid value of from 30 mgKOH/g to 150 mgKOH/g, more preferably from 35 mgKOH/g to 120 mgKOH/g, and a weight average molecular weight. Mw is preferably from 2,000 to 50,000, and more preferably from 3,000 to 30,000.

Specific examples which may be used include an epoxy ring which is reactive with an OH group between an unsaturated bond group between carbon atoms and 2-hydroxyethyl acrylate and methacrylic acid and a monomer copolymerizable therewith (such as A compound obtained by reacting a copolymer of an acrylic compound or a vinyl group-based compound to obtain a compound (for example, a compound such as glycidyl acrylate). As the reactivity with respect to the OH group, a compound having an acid anhydride other than the epoxy group, the isocyanate group or the acrylonitrile group can be used. An unsaturated carboxylic acid such as acrylic acid is reacted with a compound having an epoxy group as described in JP-A No. 6-102669, JP-A No. 6-1938 to obtain a compound such that a saturated or unsaturated polybasic acid anhydride is obtained. Reaction with the compound provides a useful reactant. Further, the repeating unit having a polymerizable group of the alkali resin having a polymerizable double bond preferably accounts for 5% by mass to 60% by mass of the resin, more preferably 10% by mass to 40% by mass.

Examples of the compound having an alkali-soluble group such as a COOH group and having an unsaturated group between carbon and carbon include DIANAL NR SERIES (trade name) (manufactured by Mitsubishi Layon); PHOTOMER 6173 (trade name) (containing COOH group) Polyurethane acrylate oligomer, manufactured by Diamond Shamrock Co., Ltd.; BISCOAT R-264, KS RESISTER 106 (trade name) (manufactured by Osaka Organic Chemical Industries Ltd.); EBECRYL 3800 (trademark) Name) (manufactured by Daicel UCB Co., Ltd.); and the like.

Other preferred alkali-soluble resins which may be used in the present invention other than the (B) resin having the (E) component include modified (meth)acrylic acid alkyl ester or styrene with (meth)acrylic acid glycidyl ester A resin obtained from a copolymer of acrylic acid. The alkyl (meth)acrylate is preferably a (meth) acrylate having 1 to 10 carbon atoms. Examples of the alkyl (meth)acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, (A) 2-ethylhexyl acrylate, benzyl (meth) acrylate and the like.

(E3-3) Other colorants

The black curable composition according to the third aspect of the present invention may further contain a coloring agent other than the inorganic pigment such as a known (F3) organic pigment or dye to exhibit desired light-shielding properties.

Examples of the (E3-3) other coloring agent used in combination with the inorganic pigment are the same as those used in the first aspect of the invention as (E1-2) other coloring agents, and the details thereof (including the preferred range) are also the same.

When the organic pigment is added to the black curable composition according to the third aspect of the invention, the amount of the organic pigment added is preferably 5% by mass to 50% by mass based on the total solid content of the black curable composition, and More preferably, it is 10% by mass to 30% by mass.

The organic pigment can be prepared by dispersion together with an inorganic pigment, or can be prepared by adding a dispersant while dispersing with a dispersant.

Examples of the dispersant (pigment dispersant) which can be used in the preparation of the organic pigment dispersion of the present invention include a polymer dispersant (for example, polyamine-amine and a salt thereof, a polycarboxylic acid and a salt thereof, and a polymer unsaturated). Acid esters, modified polyurethanes, modified polyesters, modified poly(meth)acrylates, (meth)acrylic copolymers, naphthalene-sulfonic acid-formalin condensates, and polyethylene oxide Alkyl phosphates, polyoxyethylenes, alkylamines, alkanolamines, pigment derivatives and the like.

From the viewpoint of the structure of the polymer dispersant, the polymer dispersant is classified into a linear polymer, a terminal modified polymer, a graft polymer, and a block polymer.

The polymeric dispersant functions to adsorb to the surface of the pigment and prevent re-aggregation. Thus, the polymeric dispersant comprises a terminally modified polymer, a grafted polymer, and a block polymer having a portion anchored on the surface of the pigment as a preferred structure. On the other hand, the pigment derivative reforms the surface of the pigment to achieve a function of facilitating absorption of the polymer dispersant.

Specific examples of pigment dispersants that can be used in the third aspect include: "DISPERBYK-101 (polyamine-amine phosphate), 107 (carboxylate), 110 (acid group-containing copolymer), 130 (polyamide), 161, 162, 163, 164, 165, 166, 170 (high molecular weight copolymer), "BYK-P104 and P105 (high molecular weight unsaturated polycarboxylic acid)", manufactured by BYK Chemie GmbH; "EFKA 4047, 4050, 4010, 4165 (polyurethane compound) , EFKA 4330, 4340 (block copolymer), 4400, 4402 (modified polyacrylate), 5010 (polyester decylamine), 5765 (high molecular weight polycarboxylate), 6220 (fatty acid polyester), 6745 (phthalocyanine derivative), 6750 (azo pigment derivative), manufactured by EFKA; "AJISPER PB821, PB822", manufactured by Ajinomoto Fine Techno Co., Inc.; "FLOWLEN TG-710 (amine group A) Acid ester oligomer), "POLYFLOW 50E, 300 (acrylate copolymer)", manufactured by Kyoeisha Chemical Co., Ltd.; "DISPARLON KS-860, 873SN, 874, 2150 (aliphatic polyvalent carboxylic acid) ), 7004 (polyether ester), DA-703-50, DA-705, DA-725", manufactured by Kusumoto Chemicals Ltd.; "DEMOL RN, N (naphthalenesulfonic acid-formalin polycondensation product), MS, C, SN-B (aromatic sulfonate -Fomalin polycondensation product)", "HOMOGENOLL-18 (polymer polycarboxylic acid)", "EMULGEN 920, 930, 935, 985 (polyoxyethylene nonylphenyl ether)", "ACETAMIN 86 (stearylamine) Acetate), manufactured by Kao Corporation; SOLSPERSE 5000 (phthalocyanine derivative), 22000 (azo pigment derivative), 13240 (polyesteramine), 3000, 17000, 27000 (having functional groups at the terminal) Polymer), 24000, 28000, 32000, 38500 (graft polymer)", manufactured by Lubrizol Corporation; and "NIKKOL T106 (polyoxyethylene sorbitan monooleate) and MYS-IEX (polyoxyethylene) Monostearate), which is manufactured by Nikko Chemicals Co., Ltd.

The dispersing agent may be used singly or in combination of two or more kinds of dispersing agents. In the third aspect of the invention, a combination of a pigment derivative and a polymeric dispersant is preferably used.

The content of the dispersant used in the third aspect of the invention is preferably from 1% by mass to 100% by mass, more preferably from 3% by mass to 100% by mass, based on the (F3) organic pigment, and The optimum is from 5% by mass to 80% by mass.

Specifically, in the case of using a polymer dispersant, it is preferably used in an amount of from 5% by mass to 100% by mass based on the pigment, and more preferably from 10% by mass to 80% by mass. In the case of using a pigment derivative, it is used in an amount of 1% by mass to 30% by mass, more preferably 3% by mass to 20% by mass, and most preferably 5% by mass to 15% by mass.

(E3-3) sensitizer

The black curable composition according to the third aspect of the present invention may further contain a sensitizer for the purpose of improving the radical generating efficiency of the polymerization initiator and increasing the wavelength of the photosensitive wavelength.

The sensitizer (E3-3) used in the black curable composition according to the third aspect of the present invention has the same definition as the (E1-3) sensitizer used in the first aspect, and the details thereof ( The best range is included).

(E3-4) Polymerization inhibitor

The light-shielding curable composition according to the third aspect of the present invention preferably contains a polymerization inhibitor to inhibit polymerization of the polymerizable compound during preparation or storage of the composition.

The (E3-4) polymerization inhibitor used in the third aspect has the same definition as the (E1-4) polymerization inhibitor used in the first aspect, and the details (including the preferred range) are also the same.

(E3-5) Adhesion Promoter

An adhesion promoter may be added to the light-shielding curable composition according to the third aspect of the present invention to improve the adhesion to the surface of a hard material such as a support.

(E3-5) Examples of the adhesion promoter are the same as the examples of the (E1-5) adhesion promoter used in the first aspect, and the details (including the preferred range) are also the same.

Specifically, in the case where a wafer-level lens is formed on a glass substrate by using the black curable composition according to the third aspect of the present invention, it is preferable to add an adhesion promoter from the viewpoint of sensitivity improvement.

(E3-6) surfactant

The black curable composition according to the third aspect of the present invention may further comprise any of various surfactants from the viewpoint of further improving coating properties. The surfactant used in the third aspect has the same definition as the (E2-6) surfactant used in the second aspect, and the details (including the preferred range) are also the same.

(K) other components

The black curable composition according to the third aspect of the present invention may further comprise a co-sensitizer for the purpose of, for example, additionally improving the sensitivity of the sensitizing dye or initiator to effective radiation or preventing oxygen from inhibiting polymerization of the photopolymerizable compound. Further, known additives such as a diluent, a plasticizer or a sensitizer may be added as appropriate to improve the physical properties of the cured film.

(L) organic solvent

The black curable composition according to the third aspect of the present invention can be produced using an organic solvent. The organic solvent is not particularly limited as long as the solubility or coating characteristics of the components of the colored curable composition are satisfied; however, in particular, the solubility of the ultraviolet absorber, the binder, and the coating are preferably considered. Choose organic solvents for properties and safety. In order to obtain a color hardening composition according to the third aspect of the present invention, at least two organic solvents are preferably used.

Examples of the organic solvent include: esters such as ethyl acetate, n-butyl acetate, amyl formate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, lactate Ester, ethyl lactate, alkyl oxyacetate (such as methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (such as methyl methoxyacetate, ethyl methoxyacetate, methoxyacetic acid) Butyl ester, methyl ethoxyacetate, ethyl ethoxyacetate), alkyl 3-oxopropionate (eg methyl 3-oxypropionate, ethyl 3-oxypropionate (eg 3- Methyl methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate), alkyl 2-oxopropionate (for example Methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate (eg methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2- Propyl methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate), methyl 2-oxy-2-methylpropanoate and 2-oxy-2 -ethyl methacrylate (eg methyl 2-methoxy-2-methylpropanoate, 2-ethoxy-2-methylpropionic acid) Ethyl ester), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetate, ethyl acetate, methyl 2-butoxybutanoate, ethyl 2-oxobutanoate And ethers, such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol methyl ether, ethylene glycol ethyl ether, diethylene glycol monomethyl ether, two Ethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether acetate; and a ketone such as methyl ethyl Ketones, cyclohexanone, 2-heptanone and 3-heptanone; and aromatic hydrocarbons such as toluene and xylene.

It is preferred to mix two or more kinds of the solvents in view of the ultraviolet absorbability and the solubility of the alkali-soluble resin, the improvement of the surface of the coating layer, and the like. In this case, a mixed solution of two or more solvents selected from the following solvents is particularly preferred: methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethylene glycol acetate, Ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate, propylene glycol Methyl ether and propylene glycol methyl ether acetate.

The content of the organic solvent in the colored curable composition is preferably adjusted so that the concentration of the total solid content of the composition is preferably from 5% by mass to 80% by mass, more preferably from the viewpoint of coating properties. 5% by mass to 60% by mass, and most preferably 10% by mass to 50% by mass.

The black curable composition according to the third aspect of the present invention can be polymerized by (A3) an inorganic pigment (preferably in the form of a pigment dispersion type composition containing a pigment dispersant), (B3) a specific resin, or (C3). The initiator, the (D3) polymerizable compound, and optionally various additives are added to the solvent and further mixed with an optional additive such as a surfactant to produce.

The black curable composition according to the third aspect of the present invention has a composition as described above, and thus, by hardening it with high sensitivity, a light-shielding film having excellent light-shielding properties can be formed. Further, by using the (E3-1) alkali-soluble resin which is different from the resin of the component (B3) in combination, a highly precise light-shielding pattern is formed.

Wafer-level lens according to the first and third aspects

The wafer-level lens according to the first and third aspects of the present invention has at least a black curable composition using the first aspect or the third aspect of the present invention on the peripheral portion of the lens present on the substrate. A light-shielding film.

Hereinafter, a wafer level lens according to a first aspect or a third aspect of the present invention will be described with reference to the drawings.

1 is a plan view illustrating an example of a configuration of a wafer level lens array having a plurality of wafer level lenses.

As shown in FIG. 1, the wafer level lens array has a substrate 10 and a lens 12 disposed on the substrate 10. Here, although the plurality of lenses 12 are disposed on the substrate 10 in a two-dimensional manner in FIG. 1, they may be disposed in a one-dimensional manner.

2 is a cross-sectional view taken along line A-A of the wafer level lens array shown in FIG. 1.

As shown in FIG. 2, the wafer level lens array includes a substrate 10 and a plurality of lenses 12 disposed on the substrate 10. A plurality of lenses 12 are disposed on the substrate 10 in a one-dimensional manner or in a two-dimensional manner. That is, the light blocking film 14 that blocks light from passing through the portion other than the lens 12 is provided between the plurality of lenses 12 disposed on the substrate 10.

The wafer level lens according to the first aspect or the third aspect of the present invention is composed of a lens 12 on the substrate 10 and a light-shielding film 14 provided in the peripheral portion. The light-shielding film 14 is formed using the black curable composition of the present invention.

In this embodiment, as shown in FIG. 1, a configuration in which a plurality of lenses 12 are two-dimensionally disposed on a substrate 10 is described. The lens 12 is made of the same material as the substrate 10, and thus integrally formed on the substrate 10, or is fixed to the substrate after being formed in a separate structure.

Although the examples are shown herein, the wafer level lens of the present invention is not limited to the described aspects, but may have various aspects, such as having a plurality of layered structures, or dividing into lens modules by division.

An example of a material forming the lens 12 includes glass. Glass has many types Type, and a glass having a high refractive index can be selected, and thus it is suitable for a material of a lens to be highly refractive. In addition, glass has an excellent heat resistance and is advantageous in that it can withstand reflow bonding to a photographing unit.

Another example of the material forming the lens 12 comprises a resin. The resin is easy to process and thus is suitable for forming a lens surface in a simple manner and at a low cost using a mold or the like.

In order to form a wafer level lens, an energy curable resin is preferably used. The energy curable resin may include a thermosetting resin or a resin which is hardened by irradiation with active energy such as irradiation heat, ultraviolet light, and electron beam.

In view of the fact that the reflow is adhered to the photographing unit, the softening temperature is relatively high, for example, a resin of 200 ° C or more is preferable, and a resin having a softening temperature of 250 ° C or more is more preferable.

Hereinafter, a resin suitable for a lens material will be described.

Examples of the ultraviolet curable resin include an ultraviolet curable resin, an ultraviolet epoxy resin, and an acrylic resin. As the epoxy resin, an epoxy resin having a linear expansion coefficient of 40 to 80 [10 ^-6 /K] and a refractive index of 1.50 to 1.70, and preferably 1.50 to 1.65 can be used.

Examples of the thermosetting resin include a thermosetting resin, a thermosetting epoxy resin, a thermosetting phenol resin, and a thermosetting acrylic resin. For example, as the oxime resin, a ruthenium resin having a linear expansion coefficient of 30 to 160 [10 ^-6 /K] and a refractive index of 1.40 to 1.55 can be used. As the epoxy resin, an epoxy resin having a linear expansion coefficient of 40 to 80 [10 ^-6 /K] and a refractive index of 1.50 to 1.70, and preferably 1.50 to 1.65 can be used.

As the phenol resin, a phenol resin having a linear expansion coefficient of 30 to 70 [10 ^-6 /K] and a refractive index of 1.50 to 1.70 can be used. As the acrylic resin, an acrylic resin having a linear expansion coefficient of 20 to 60 [10 ^-6 /K] and a refractive index of 1.40 to 1.60, and preferably 1.50 to 1.60 can be used.

Examples of the thermosetting resin include an epoxy resin, a siloxane resin, and the like. Commercially available products can be used as the thermosetting resin, and examples thereof include SMX-7852 and SMX-7877. (trade name, manufactured by Fuji Polymer Industries Co., Ltd.), IVSM-4500 (trade name, manufactured by TOSHIBA CORPORATION), SR-7010 (trade name, manufactured by Dow Corning Toray Co., Ltd.).

Examples of the thermoplastic resin include polycarbonate resin, polyfluorene resin, polyether oxime resin, and the like. As the polycarbonate resin, a polycarbonate resin having a linear expansion coefficient of 60 to 70 [10 ^-6 /K] and a refractive index of 1.40 to 1.70, and preferably 1.50 to 1.65 can be used. As the polyfluorene resin, a polyfluorene resin having a linear expansion coefficient of 15 to 60 [10 ^-6 /K] and a refractive index of 1.63 can be used. As the polyether oxime resin, a polyether oxime resin having a linear expansion coefficient of 20 to 60 [10 ^-6 /K] and a refractive index of 1.65 can be used.

In general, the linear expansion coefficient of the optical glass is 4.9 to 14.3 [10 ^-6 /K] at 20 ° C, and its refractive index is 1.4 to 2.1 at a wavelength of 589.3 nm. Similarly, quartz glass has a linear expansion coefficient of 0.1 to 0.5 [10 ^-6 /K] and a refractive index of about 1.45.

From the viewpoint of molding (such as transfer suitability for a mold shape), the curable resin composition suitable for forming a lens preferably has a suitable fluidity before hardening. In particular, the curable resin composition is preferably liquid at room temperature and has about 1000 mPa. Seconds to 50,000 mPa. The viscosity of seconds.

The curable resin composition suitable for forming the lens preferably has a heat resistance which does not undergo thermal deformation throughout the reflow process after hardening. From the viewpoint of the viewpoint, the glass transition temperature of the hardened material is preferably 200 ° C or higher, more preferably 250 ° C or higher, and most preferably 300 ° C or higher. In order to impart high heat resistance to the resin composition, it is necessary to limit mobility at the molecular level, and examples of means suitable for the purpose include: (1) a manner of increasing the crosslinking density per unit volume; and (2) having a resin of a rigid ring structure (for example, a resin having the following structure: an alicyclic structure (such as cyclohexane, norbornane, tetracyclododecane); an aromatic structure (such as benzene and naphthalene); a cardo Structure (such as 9,9'-biphenyl fluorene); spiro structure (such as spirobiindane), and specific examples thereof include JP-A No. 9-137043, JP-A No. 10-67970, JP -A No. 2003-55316, JP-A No. 2007-334018, JP-A No. 2007-238883, and the like); (3) will have A method in which a material of a high Tg such as inorganic fine particles is uniformly dispersed (for example, a method disclosed in JP-A No. 5-209027, JP-A No. 10-298265); and the like. The means can be used in combination, and preferably within a range that does not affect other features such as flow, shrinkage or refractive index.

From the viewpoint of shape transfer accuracy, a resin composition having a low volume shrinkage due to a hardening reaction (specifically, a curable resin composition having a low volume shrinkage due to a hardening reaction) is preferred. The resin composition used in the first aspect or the third aspect of the invention preferably has a curing shrinkage ratio of 10% or less, more preferably 5% or less, and most preferably 3% or less.

Examples of the resin composition having a low hardening shrinkage ratio include (1) a resin composition containing a polymerization hardener (prepolymer or the like) (polymerization hardener is, for example, JP-A No. 2001-19740, JP-A) The number average molecular weight of the polymeric hardener is preferably in the range of 200 to 100,000, more preferably 500 to 50,000, and most preferably disclosed in JP-A No. 2007-211247 or the like. Preferably, the calculated value of the number average molecular weight/hardening reactive group of the hardener is preferably in the range of 50 to 10,000, more preferably 100 to 5,000, and most preferably 200 to 3,000); 2) Containing an unreactive material (organic/inorganic fine particles, an unreactive resin, or the like) (for example, JP-A No. 6-298883, JP-A No. 2001-247793, JP-A No. 2006-225434 The resin composition of the present invention or the like (3) comprises the following resin composition: a low-shrinkage crosslinking reactive group (for example, a ring-opening polymerizable group (for example, JP-A No. 2004- Or a heterocyclic butyl group (for example, as disclosed in JP-A No. 8-134405); an episulfide compound; a group (for example, as disclosed in JP-A No. 2002-105110 or the like); a cyclic carbonate group (for example, JP-A No. 7-62065 or the like), etc.; enol/sulfur An alcohol hardening group (for example, those disclosed in JP-A No. 2003-20334 or the like); a hydrogenated hardening group (for example, as disclosed in JP-A No. 2005-15666 or the like), and the like) (4) Contains a rigid skeleton resin (fluorine, adamantane, isophorone, and the like) (for example, as disclosed in JP-A No. 9-137043) Or a resin thereof; (5) a resin composition forming an interpenetrating polymer network structure (so-called IPN structure) containing two monomers having different polymerizable groups (for example, JP-A No. (6) Including an expansive material (for example, as disclosed in JP-A No. 2004-2719, JP-A No. 2008-238417 or the like) The resin composition or the like can be suitably used in the present invention. Also, from the viewpoint of optimizing physical characteristics, it is preferred to use a plurality of methods for reducing hardening shrinkage (for example, a prepolymer containing a ring-opening polymerizable group and a resin composition containing fine particles).

In forming the wafer level lens of the present invention, it is preferred to use a composition containing two or more resins having different relatively high Abbe numbers and relatively low Abbe numbers.

The Abbe number (υd) of the resin having a relatively high Abbe number is preferably 50 or more, more preferably 55 or more, and most preferably 60 or more. The refractive index (nd) of the resin is preferably 1.52 or more, more preferably 1.55 or more, and most preferably 1.57 or more.

The resin is preferably an aliphatic resin, and particularly preferably a resin having an alicyclic structure (for example, having a ring structure such as cyclohexane, norbornane, adamantane, tricyclodecane, tetracyclododecane) Resins, in particular, for example, JP-A No. 10-152551, JP-A No. 2002-212500, JP-A No. 2003-20334, JP-A No. 2004-210932, JP-A No. 2006-199790 No. 2007-2144, JP-A No. 2007-284650, JP-A No. 2008-105999, or the like.

The Abbe number (υd) of the resin having a relatively low Abbe number is preferably 30 or less, more preferably 25 or less, and most preferably 20 or less. The refractive index (nd) of the resin is preferably 1.60 or more, more preferably 1.63 or more, and most preferably 1.65 or more.

The resin is preferably a resin having an aromatic structure, and for example, the resin preferably contains a resin containing a structure such as 9,9'-diarylsulfonium, naphthalene, benzothiazole, and benzotriazole (specifically, For example, JP-A No. 60-38411, JP-A No. 10-67977, JP-A No. 2002-47335, JP-A No. 2003-238884, JP-A No. 2004-83855, JP- A No. 2005-325331, JP-A No. 2007-238883, International Publication No. Resin disclosed in Japanese Patent No. 2537540 or the like).

The resin composition for forming a wafer level lens preferably comprises an organic and inorganic composite material which is formed by dispersing inorganic fine particles in a matrix for the purpose of increasing the refractive index or adjusting the Abbe number.

Examples of the inorganic fine particles in the organic-inorganic composite material include oxide fine particles, sulfide fine particles, selenide fine particles, and telluride fine particles. In the first aspect, specific examples of the inorganic fine particles include fine particles such as zirconia, titanium oxide, zinc oxide, tin oxide, and zinc sulfide. In the first and third aspects, more specific examples include particles such as zirconia, titania, zinc oxide, tin oxide, cerium oxide, cerium oxide, aluminum oxide, cerium oxide, cerium oxide, and zinc sulfide.

Specifically, in the first aspect, particles such as cerium oxide, aluminum oxide or zirconium oxide are preferably dispersed in a resin having a high Abbe number, and preferably such as titanium oxide, tin oxide or zirconium oxide. The particles are dispersed in a resin having a low Abbe number.

In the first and third aspects, the inorganic fine particles may be used singly or in combination of two or more kinds of fine particles. Composite materials having a plurality of components can be used.

To achieve various purposes (such as reducing photocatalytic activity, lowering the absorption ratio, or the like), doping the heterogeneous metal into the inorganic fine particles, or coating the surface of the inorganic fine particles with a heterogeneous metal oxide such as ceria or alumina. Alternatively, the surface may be modified with a decane coupling agent, a titanate coupling agent or a dispersing agent having an organic acid (carboxylic acid, sulfonic acid, phosphoric acid, phosphonic acid or the like) or having an organic acid group.

The number of inorganic particles generally has an average initial particle size of about 1 nm to 1000 nm; however, if the size is too small, there is a condition in which the physical characteristics of the material change, and if it is too large, the Rayleigh scattering is significantly affected. Therefore, the size is preferably from 1 nm to 15 nm, more preferably from 2 nm to 10 nm, and most preferably from 3 nm to 7 nm. In the present invention, the particle size distribution of the inorganic fine particles is relatively narrow. Although the methods for defining the monodisperse particles are different, the numerical definition range disclosed in JP-A No. 2006-160992 corresponds to a preferred particle diameter distribution range.

The number average primary particle size can be measured using, for example, an X-ray diffraction (XRD) element or a transmission electron microscope (TEM) or the like.

The refractive index of the inorganic fine particles is preferably 1.90 to 3.00, more preferably 1.90 to 2.70, and most preferably 2.00 to 2.70 at a wavelength of 22 ° C and 589.3 nm.

The content of the inorganic fine particles in the resin is 5% by mass or more, more preferably 10% by mass to 70% by mass, and most preferably 30% by mass to 60% by mass, from the viewpoint of transparency and high refractive index.

As a matrix-based resin for organic and inorganic composite materials, an ultraviolet curable resin, a thermosetting resin, a thermoplastic resin, a resin having a high Abbe number, and a resin having a low Abbe number can be used as a wafer-level lens material. Either. Further, examples thereof include a resin having a refractive index of more than 1.60 as disclosed in JP-A No. 2007-93893, and block copolymerization of a hydrophobic segment and a hydrophilic segment disclosed in JP-A No. 2007-211164 It is disclosed in the polymer end or the side chain as disclosed in JP-A No. 2007-238929, JP-A No. 2010-0431919, JP-A No. 2010-065063, and JP-A No. 2010-054817. A resin which forms a functional group of any chemical bond with an inorganic fine particle; a thermoplastic resin disclosed in JP-A No. 2010-031186 and JP-A No. 2010-037368.

Further, an additive such as a plasticizer or a dispersant may be optionally added to the organic and inorganic composite materials.

In the third aspect, the resin is preferably combined as a matrix with inorganic fine particles as follows.

In particular, when a resin having a high Abbe number is used as a substrate, particles such as cerium oxide, aluminum oxide or zirconium oxide are preferably dispersed therein as inorganic fine particles, and when a resin having a low Abbe number is used as a substrate At this time, fine particles such as titanium oxide, tin oxide or zirconium oxide are preferably dispersed therein as inorganic fine particles.

In the first and third aspects, in order to uniformly disperse the fine particles in the resin composition, it is preferred to suitably use, for example, a dispersing agent containing a functional group reactive with the resin monomer forming the matrix (for example, JP-A No. 2007- The person disclosed in the embodiment of No. 238884 or the like a block copolymer composed of a hydrophobic segment and a hydrophilic segment (for example, as disclosed in JP-A No. 2007-211164 or the like); or having a polymer terminal or a side chain A resin which forms a functional group of any chemical bond with an inorganic fine particle (for example, those disclosed in JP-A No. 2007-238929, JP-A No. 2007-238930, or the like).

In the resin composition for forming the wafer level lens used in the present invention, an additive such as a known mold release agent such as ruthenium, fluorine, a compound containing a long-chain alkyl group or the like may be appropriately blended; Oxidation inhibitors, such as hindered phenols.

In the resin composition for forming a wafer level lens of the present invention, a hardening catalyst or an initiator may optionally be blended. Specific examples thereof include a compound which promotes a hardening reaction (radical polymerization or ionic polymerization) under the action of heat or active energy rays as disclosed in paragraphs [0065] to [0066] of JP-A No. 2005-92099 . The amount of the hardening reaction accelerator added may not be simply limited because it varies depending on the type of the catalyst or the initiator or the hardening reactive portion or the like; however, it is generally preferred that the total solid content of the hardening active resin composition is 0.1% by mass to 15% by mass, more preferably 0.5% by mass to 5% by mass.

The resin composition for forming a wafer level lens of the present invention can be prepared by appropriately blending the components. At this time, although it is not necessary to add a separate solvent in the case where other components are soluble in the liquid low molecular monomer (reactive diluent) or the like, it may be borrowed without corresponding to the situation. The resin composition was prepared by dissolving each component using a solvent. The solvent to be used in the resin composition is not particularly limited, and may be appropriately selected as long as the composition is uniformly dissolved or dispersed without precipitation, and specific examples thereof include a ketone (for example, acetone, methyl ethyl ketone, methyl isoform). Butyl ketone and the like), esters (such as ethyl acetate, butyl acetate and the like), ethers (such as tetrahydrofuran, 1,4-dioxane and the like), alcohols (such as methanol, ethanol, Isopropanol, butanol, ethylene glycol, and the like), aromatic hydrogencarbonates (e.g., toluene, xylene, and the like), water, and the like. In the case where the resin composition contains a solvent, it is preferred to carry out a mold shape transfer operation after casting the composition on a substrate and/or a mold to dry the solvent.

Wafer-level lenses forming first and third aspects

The substrate 10 may be formed of the same material as the molding material of the lens 12. The substrate 10 may be formed of a material different from the molding material of the lens 12 as long as the substrate 10 is formed of a material transparent to visible light such as glass. In this case, the material forming the substrate 10 preferably has the same or substantially the same linear expansion coefficient as the material forming the lens 12. In the case where the linear expansion coefficient of the material forming the lens 12 is the same as or substantially the same as the linear expansion coefficient of the material forming the substrate 10, the lens 12 can be prevented from being heated when the wafer-level lens is reflow-bonded to the photographing unit. Deformation or cracking due to the difference in linear expansion ratio during the period.

Further, an infrared filter (IR filter) (not shown in FIGS. 1 and 2) may be formed on the surface of the light incident side of the substrate 10.

Hereinafter, with reference to FIGS. 3 through 8C, the configuration and preparation of wafer level lenses will be specifically described by reference to a method of producing a wafer level lens array.

[Configuration and Preparation of Wafer Level Lens (1)]

First, a method of forming the lens 12 on the substrate 10 will be described with reference to FIGS. 3, 4A to 4C.

Fig. 3 illustrates a supply state of a molding material (indicated by M in Fig. 3) which is a resin composition for forming a lens on a substrate.

4A through 4C illustrate the order in which the lens 12 is molded on the substrate 10 using the mold 60.

As shown in FIG. 3, the molding material M is dropped onto the portion of the substrate 10 on which the lens is formed using the dispenser 50. Here, the molding material M corresponding to the amount of one lens 12 is supplied on one portion.

After the molding material M is supplied onto the substrate 10, the mold 60 for forming a lens is placed on the substrate 10 as shown in FIG. 4A. The mold 60 has a plurality of concave portions 62 for transferring the shape of the lens 12 in accordance with the desired number of lenses 12.

As shown in FIG. 3, the molding material M is applied dropwise onto the portion of the substrate 10 on which the lens 12 is to be formed, using the dispenser 50. Will be required to form a lens 12 A quantity of molding material M is supplied to the portions on which the lens is to be formed.

After the molding material M is supplied onto the substrate 10, as shown in FIG. 4A, the mold 60 for forming the lens 12 is placed on the surface of the substrate 10 to which the molding material M is supplied.

A concave portion 62 for transferring the shape of the lens 12 is provided in the mold 60 in accordance with the required number of lenses 12.

Subsequently, as shown in FIG. 4B, the mold 60 is pressed to the molding material M on the substrate 10 to deform the molding material M according to the shape of the concave portion 62. Next, when the molding material M is a thermosetting resin or an ultraviolet curable resin, the molding material M is hardened by irradiating heat or ultraviolet light from the outside of the mold 60 while pressing the mold 60 to the molding material M.

After the molding material M is hardened, the mold 60 is removed from the substrate 10 and the lens 12 as shown in FIG. 4C.

[Formation of a light-shielding film]

A method of forming the light-shielding film 14 in the peripheral portion of the lens 12 will be described with reference to FIGS. 5A to 5C.

5A to 5C are schematic cross-sectional views showing the steps of forming the light-shielding film 14 on the substrate 10 on which the lens 12 has been formed.

In the first and third aspects, the method of forming the light-shielding film 14 includes applying the black curable composition of the present invention to the substrate 10 to form the light-shielding coating layer 14A (hereinafter, it may be referred to as "shading property". Coating forming step" or "shading hardenable composition coating forming step" (see FIG. 5A); pattern exposure of the light-shielding coating 14A via the mask 16 (hereinafter, may be referred to as "exposure step") (See FIG. 5B); and developing the light-shielding coating layer 14A after exposure, and removing the uncured portion thereof to form a patterned light-shielding film 14 (hereinafter, may be referred to as "development step") (see FIG. 5C) .

The patterned light-shielding film 14 can be formed arbitrarily before or after the lens 12 is formed. Hereinafter, a method of forming a patterned light-shielding film after the lens 12 has been formed will be described. law.

The respective steps of the method of forming the light-shielding film 14 will be described below.

Black hardening composition coating forming method

In the black curable composition coating forming method (or the light-shielding coating forming step), as shown in FIG. 5A, a black curable composition is applied onto the substrate 10 to form a black curable composition. A light-shielding coating 14A having a low light reflection coefficient. In this case, the light-shielding coating layer 14A is formed to cover the surface of the substrate 10 and the lens surface 12a of the lens 12 and the surface 12b of the peripheral portion of the lens.

The substrate 10 usable in this step is not particularly limited. Examples of the substrate 10 include soda glass, PYREX (registered trademark) glass, quartz glass, and a transparent resin. In the third aspect, in addition to this, examples thereof include alkali-free glass.

In the embodiment in which the lens 12 is integrally formed with the substrate 10, the "substrate 10" refers to a configuration having the lens 12 and the substrate 10.

On the substrate 10, an undercoat layer may optionally be provided to improve the adhesion to the upper layer, to prevent diffusion of the material or to flatten the surface of the substrate 10.

Examples of the method of applying the black curable composition to the substrate 10 and the lens 12 include various coating methods such as a slit coating method, a spray coating method, an inkjet method, a spin coating method, a cast coating method, a roll coating method, or a net method. Printing method.

The film thickness immediately after the application of the black curable composition is preferably from 0.1 μm to 10 μm, more preferably from 0.2 μm to 5 μm, even from the viewpoint of uniformity of coating film thickness and easy drying of the coating solvent. More preferably, it is 0.2 micrometers to 3 micrometers.

The black layer (light-blocking hardenable composition coating layer) 14A coated on the substrate 10 can be dried (prebaked) at a temperature of 50 ° C to 140 ° C for 10 seconds to 300 seconds using, for example, a hot plate or an oven.

The film thickness after drying of the black curable composition (hereinafter also referred to as "dry film thickness") can be arbitrarily selected depending on the desired performance (such as light-shielding property), and is generally in the range of 0.1 μm to 50 μm or less.

Exposure process

In the exposure step, the light-shielding coating layer 14A formed in the light-shielding coating layer forming step is subjected to pattern exposure. Pattern exposure can be performed by scanning exposure, but as shown in FIG. 5B, exposure is preferably performed via a mask 70 having a specified mask pattern.

In the exposure steps of the first and third aspects, the light-shielding coating layer 14A is exposed through a mask having a prescribed mask pattern, whereby the portion of the light-shielding coating layer 14A that is only irradiated with light is hardened. Light illuminates the surface of the lens peripheral portion 12b and the surface of the substrate 10 existing between the lenses 12 via the mask pattern used. Therefore, only the light-shielding coating layer 14A existing in the region other than the lens surface 12a is hardened by light irradiation, and the hardened region forms the light-shielding film 14.

As the radiation which can be used for exposure, ultraviolet rays such as g-rays, h-rays and i-rays are preferably used. The radiation may be from a single wavelength source or may be from a source containing all wavelengths, such as a high pressure mercury gas lamp.

Developing process

Subsequently, by performing an alkali development treatment (development step), the portion of the light-shielding coating layer 14A which is not irradiated with light during the exposure (that is, the unhardened portion) is dissolved in the aqueous alkali solution, and only the region irradiated with light is retained. The hardened portion of the light-shielding coating 14A.

Specifically, when the exposed light-shielding coating layer 14A is developed as shown in FIG. 5B, as shown in FIG. 5C, only the portion of the light-shielding coating layer 14A formed on the lens surface 12a is removed, and hardening shading is performed. The film 14 is formed in a region other than the region where the light-shielding coating layer 14A has been removed.

The alkali agent contained in the developer (aqueous alkali solution) used in the development step may be any one of an organic base agent, an inorganic alkali agent, and a combination of an organic base agent and an inorganic base agent. From the viewpoint of reducing the possibility of damaging the peripheral circuit, it is preferred to use an organic alkali developer in forming the light-shielding film of the present invention.

Examples of the alkali agent used in the developer include: an organic base compound (organic alkali agent) such as ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, Tetraethylammonium hydroxide, choline, pyrrole, piperidine or 1,8-diazabicyclo-[5,4,0]-7-undecene; and inorganic compounds (inorganic alkaline agents) such as hydroxide Sodium, potassium hydroxide, sodium bicarbonate or potassium bicarbonate. The aqueous alkali solution diluted with pure water is used as a developer, so that the concentration of the alkali agent is from 0.001% by mass to 10% by mass, and preferably from 0.01% by mass to 1% by mass.

The development is carried out at a temperature of from 20 ° C to 30 ° C for from 20 seconds to 90 seconds.

In the case where a developer formed of an aqueous alkali solution is used, the unexposed portion of the coated film is generally removed by the developer, followed by washing (rinsing) with pure water. In other words, after the development treatment, excess developer is satisfactorily washed away and removed with pure water, and then a drying step is performed.

In one embodiment, the preparation method may optionally include a step of hardening the formed light-shielding film (light-shielding pattern) by heating (post-baking) and/or exposure after performing the coating forming step, the exposing step, and the developing step.

Post-baking is a heat treatment for the purpose of achieving complete hardening after development, and is generally a heat hardening treatment performed at 100 ° C to 250 ° C. The conditions for post-baking (such as temperature and time) can be appropriately set depending on the material of the substrate 10 or the lens. For example, in the case where the substrate 10 is glass, the post-baking temperature is preferably from 180 ° C to 240 ° C.

The developed light-shielding film 14 may be subjected to a post-baking treatment in a continuous system or a batch system using a heating device such as a hot plate, a convection oven (hot air circulation dryer) or a high frequency heating device so as to have a suitable state.

In the above, an embodiment in which the lens 12 has a concave shape is described. However, the shape of the lens is not particularly limited thereto, and the lens may have a convex or aspherical surface. Further, in the above, an embodiment in which the wafer level lens has a plurality of lenses 12 formed on one side of the substrate 10 is described. However, the wafer level lens of the present invention may have a configuration in which a plurality of lenses 12 are formed on both sides of the substrate 10, and in this case, a light shielding layer 14 (for example, a patterned light shielding film) is formed on the substrate 10 In the area other than the lens surface on the side.

[Configuration and generation of wafer level lens (2)]

6 is a cross-sectional view showing another configuration example of a wafer level lens array.

The wafer level lens array shown in FIG. 6 has a configuration (integral type) in which the substrate 10 and the lens 12 are simultaneously formed using the same molding material.

Examples of molding materials used to form such wafer level lens arrays are the same as those described above. In this embodiment, a plurality of concave lenses 12 are formed on one side (upper side in the drawing) of the substrate 10, and a plurality of convex lenses 20 are formed on the other side (lower side in the drawing) of the substrate. The patterned light-shielding film 14 is formed in a region other than the lens surface 12a of the substrate 10; that is, the patterned light-shielding film 14 is formed on the surface of the substrate 10 and on the surface 12b of the peripheral portion of the lens. As the patterning method for forming the light-shielding film 14, any of the methods described above can be used.

[Configuration and generation of wafer level lens (3)]

Referring to FIGS. 7A to 7C and FIGS. 8A to 8C, another configuration example of a wafer level lens array and a procedure for preparing the same will be described below.

7A through 7C are schematic views showing another embodiment of a method of forming the patterned light-shielding film 14.

8A to 8C are schematic views showing a method of forming the lens 12 after the patterned light-shielding film 14 has been formed.

In the embodiment of the wafer level lens array shown in FIGS. 3 through 6, a patterned light-shielding film 14 is formed on the substrate 10 on which the lens 12 has been formed. On the other hand, in the embodiment described below, first, the patterned light-shielding film 14 is formed on the substrate 10, and then the lens 12 is formed on the substrate 10.

[Formation of a light-shielding film]

First, as shown in FIG. 7A, a black curable composition is applied onto the substrate 10 to form a light-shielding coating layer 14A (hereinafter, may be referred to as a "light-shielding coating forming step").

Subsequently, the light-shielding coating layer 14A coated on the substrate 10 is dried using, for example, a hot plate or an oven at a temperature of 50 ° C to 140 ° C for 10 seconds to 300 seconds. The dry film thickness of the opaque coating can be selected according to the desired performance (such as shading characteristics) and is at about 0.1. Micron to a range of less than about 50 microns.

Next, as shown in FIG. 7B, the light-shielding coating layer 14A formed in the light-shielding coating layer forming step is subjected to pattern exposure through the mask 70. The mask 70 has a specified mask pattern.

During the exposure in the embodiment of the present invention, the light-shielding coating layer 14 is subjected to pattern exposure, and thereby the portion of the light-shielding coating layer 14A that is only irradiated with light is hardened. In this embodiment, the mask pattern used is capable of illuminating light at a portion of the light-shielding coating 14A that does not include the area of the lens aperture 14a used as the lens 12 when the lens 12 is formed in a subsequent process. . In this manner, the light-shielding coating layer 14A other than the portion of the lens aperture 14a of the lens 12 is hardened by light irradiation. According to the above embodiment, examples of radiation that can be used for exposure preferably include ultraviolet rays such as g-rays, h-rays or i-rays.

Next, by performing an alkali development treatment (development step), a region of the light-shielding coating layer 14A corresponding to only the lens aperture 14a of the lens 12, which is an area where the light-shielding coating layer 14A is not hardened in pattern exposure, is dissolved with an aqueous alkali solution. . At this time, as shown in FIG. 7C, the photo-curable light-shielding coating layer 14A remains on the substrate 10 except for the region for the lens aperture 14a of the lens 12, and the light-shielding film 14 is formed.

Examples of the alkali agent contained in the aqueous alkali solution used as the developer are the same as those used in the examples described above.

Next, after the development treatment, excess developer is washed and removed, followed by drying.

In an embodiment of the present invention, after performing the coating forming step (the light-shielding coating forming step), the exposing step, and the developing step, the formed light-shielding film may be formed by post-baking and/or exposure as described above. hardening.

Forming a lens

Next, the step of forming the lens 12 after the formation of the light-shielding film 14 will be described.

As shown in FIG. 8A, the molding material M for the lens 12 is applied dropwise onto the substrate 10 on which the patterned light-shielding film 14 has been formed, using the dispenser 50. The molding material M for the lens 12 is supplied to cover the region corresponding to the lens aperture 14a of the lens 12 and also covers the end portion of the light-shielding film 14 adjacent to the aperture.

After the molding material M is supplied onto the substrate 10, as shown in FIG. 8B, the mold 80 for forming a lens is placed on the side of the substrate 10 on which the molding material M has been supplied. The mold 80 has a plurality of concave sections 82 for transferring the shape of the lens 12 depending on the desired number of lenses 12.

Next, the mold 80 is pressed onto the molding material M present on the substrate 10 to deform the molding material M according to the shape of the concave section. When the molding material M is a thermosetting resin or an ultraviolet curable resin, the molding material M is hardened by irradiating heat or ultraviolet light from the outside of the mold while pressing the mold 80 onto the molding material M.

After the molding material M is hardened, as shown in FIG. 8C, the mold 80 is removed from the substrate 10 and the lens 12, thereby obtaining a wafer-level lens array having the patterned light-shielding film 14 on the substrate 10.

As described above, the patterned light-shielding film 14 to be provided in the wafer level lens is formed not only in the region other than the lens surface 12a of the lens 12 as shown in FIG. 5, but also the light-shielding film 14 can be as shown in FIG. The display in 8C is provided in a region other than the lens aperture 14a of the lens 12.

In the wafer level lens, in a region other than the lens surface 12a of the lens 12 or the lens aperture 14a, by using the light-shielding film 14 having a low light reflection coefficient patterned on at least one side of the substrate 10, It suppresses the generation of reflected light while fully exhibiting the light blocking property. Therefore, in the case where a wafer level lens is applied to a photographic module having a photographic element, defects caused by reflected light during photographing such as ghosting or reflection can be prevented.

Further, since the light-shielding film 14 is provided on the surface of the substrate, it is not necessary to place another light-shielding member in the wafer-level lens, and the production cost can be prevented from being improved.

In addition, according to the international application publication No. 2008/102648 It is configured that, with a concave and convex structure around the surface of the lens, light incident on the structure is reflected or diffused, and thus there is a risk of causing defects such as ghosting. In this regard, as shown in FIG. 2, when the patterned light-shielding film 14 is provided in a region other than the lens surface 12a of the lens 12, light other than the lens surface 12a can be shielded and optical performance can be improved.

Second aspect of the light-shielding film

Next, a light-shielding film of a second aspect of the present invention will be described.

The black curable composition using the second aspect of the present invention is a light-shielding film which forms the second aspect of the present invention on the other surface of the substrate having the photographic element unit on one surface. For the reasons described above, the light-shielding film of the present invention has excellent infrared light-shielding properties. Further, in the present invention, the residue at the vicinity of the light-shielding film (the region where the light-shielding film is not formed on the substrate) is reduced. Also, the adhesion of the light-shielding film to the substrate can be improved.

The film thickness of the light-shielding film is not particularly limited, and is preferably from 0.1 μm to 10 μm, more preferably from 0.3 μm to 5.0 μm, and most preferably from 0.5 μm to from the viewpoint of effectively achieving the effect of the present invention. 3.0 microns. The pattern size of the light-shielding film is not particularly limited, and is preferably 1000 μm or less, more preferably 500 μm or less, and most preferably 300 μm or less from the viewpoint of effectively achieving the effect of the present invention. The lower limit is preferably 1 micrometer.

The spectral characteristics of the light-shielding film of the present invention are not particularly limited, but are at 365 nm, in terms of further improving the infrared light-shielding property, the light-shielding property of the visible light region, and the light-shielding property of the infrared region, and the like. The ratio of the optical density at the wavelength (OD ₃₆₅ ) to the optical density at the wavelength of 1200 nm (OD ₁₂₀₀ ) [OD ₁₂₀₀ /OD ₃₆₅ ] is preferably 0.5 to 3.

The optical density (OD) was obtained as an OD value by using the UV-3600 measurement manufactured by Shimadzu Corporation to measure the transmittance of the film, and using the following equation B to convert the obtained transmittance (%T).

OD value = -Log(%T/100) Equation B

In the second aspect of the invention, the optical density at a wavelength of λ nm is represented by "OD _λ ".

From the viewpoint of further improving the balance between the infrared ray shielding property, the light shielding property of the visible light region, and the light shielding property of the infrared region, the optical density of the light shielding film should satisfy the following conditions from the viewpoint of effectively achieving the action of the present invention. That is, the ratio [OD ₁₂₀₀ /OD ₃₆₅ ] is more preferably 1.0 to 2.5 and most preferably 1.3 to 2.0.

The optical density [OD ₁₂₀₀ ] of the light-shielding film at a wavelength of 1200 nm is preferably from 1.5 to 10, and more preferably from 2 to 10.

The optical density (OD ₃₆₅ ) of the light-shielding film at a wavelength of 365 nm is preferably from 1 to 7, and more preferably from 2 to 6.

The optical density of the light-shielding film in the wavelength range of from 900 nm to 1300 nm is preferably from 2 to 10, more preferably from 2 to 9, and most preferably from 2 to 8.

The ratio of the light-shielding film [OD ₉₀₀ / OD ₃₆₅ ] is preferably from 1.0 to 2.5, and more preferably from 1.1 to 2.5.

The ratio of the light-shielding film [OD ₁₁₀₀ / OD ₃₆₅ ] is preferably from 0.6 to 2.5, and more preferably from 0.7 to 2.5.

The ratio of the light-shielding film [OD ₁₃₀₀ /OD ₃₆₅ ] is preferably from 0.4 to 2.3, and more preferably from 0.5 to 2.0.

The above-described detailed example of the light-shielding film of the second aspect of the present invention includes the light-shielding film described above for the application of the black curable composition of the second aspect of the present invention.

Method for preparing second-mode light-shielding film

The light-shielding film of the second aspect of the present invention is prepared by applying the above-described black curable composition of the second aspect of the present invention to the other surface of the substrate having the photographic element unit on one surface to form a black curable composition layer (hereinafter, also referred to as "photosensitive layer" or "photosensitive layer") (hereinafter, also referred to as "photosensitive layer forming process"); pattern exposure of the photosensitive layer (hereinafter, also It is called "exposure process"; and the photosensitive layer is developed after exposure to form a pattern (hereinafter, also referred to as "development process").

According to the method for producing a light-shielding film according to the second aspect of the present invention, residues in a region other than the region where the light-shielding film is formed can be reduced during formation of the light-shielding film (hereinafter, also referred to as "developing residue" ”), since the light-shielding film has excellent infrared light shielding properties, it is possible to manufacture a light-shielding film having improved adhesion to members on the side surface of the ruthenium substrate.

Hereinafter, each process in the method of producing the light-shielding color filter of the present invention will be described.

Photosensitive layer forming process

In the photosensitive layer forming process, the black curable composition of the present invention is applied onto a substrate to form a photosensitive layer.

Examples of the method of applying the black curable composition of the second aspect of the present invention to a ruthenium substrate include various coating methods such as a slit coating method, an inkjet method, a spin coating method, a cast coating method, a roll coating method, or Screen printing method.

The coating film thickness (dry film thickness) of the black curable composition is preferably from 0.35 μm to 3.0 μm, and more preferably from 0.50 μm to 2.5 μm, from the viewpoint of resolution and developability.

The black curable composition applied to the ruthenium substrate is usually dried at a temperature of 70 ° C to 130 ° C for 2 minutes to 4 minutes, and thus a photosensitive layer is formed.

Further, in the case where the black curable composition of the present invention is adhered to, for example, a nozzle of an applicator sprayer, a tube of an applicator, an inside of an applicator, and the like, it can be easily cleaned using a well-known cleaning solution. And removed. In the above case, the above-mentioned solvent contained in the black curable composition of the present invention is preferably used as a cleaning liquid for more effective cleaning and removal.

In addition, it is preferable to use JP-A No. 7-128867, JP-A No. 7-146562, JP-A No. 8-278637, JP-A No. 2000-273370, JP-A No. 2006-85140, JP. -A cleaning solution disclosed in documents such as No. 2006-291191, JP-A No. 2007-2101, JP-A No. 2007-2102, JP-A No. 2007-281523, etc. The black curable composition of the present invention is washed and removed.

Alkanediol monoalkyl ether carboxylate or alkylene glycol monoalkyl ether is preferably used as the cleaning liquid.

The solvent used as the cleaning liquid may be used singly or in the form of a mixture of two or more of them.

In the case where two or more kinds of solvents are mixed, a mixed solvent obtained by mixing a solvent having a hydroxyl group and a solvent having no hydroxyl group is preferred. The mass ratio between the solvent having a hydroxyl group and the solvent having no hydroxyl group is from 1/99 to 99/1, preferably from 10/90 to 90/10, and more preferably from 20/80 to 80/20. The mixed solvent is a mixed solvent of propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME), and the ratio is preferably 60/40.

In order to improve the permeability of the cleaning liquid to the black curable composition, the above-mentioned surfactant contained in the black curable composition may be added to the cleaning liquid.

Exposure process

In the exposure process, a photosensitive layer formed in the photosensitive layer forming process is subjected to pattern exposure using, for example, a mask. When the exposure is performed using a mask, the light-irradiated coating film is partially hardened.

The exposure is preferably performed by irradiation with radiation, and as the radiation for exposure, ultraviolet rays such as g rays, h rays or i rays are preferably used, and high pressure mercury or the like is more preferably used. The irradiation intensity is 5 mJ to 3,000 mJ, more preferably 10 mJ to 2,000 mJ, and most preferably 10 mJ to 1000 mJ.

Developing process

After the exposure process, the photosensitive layer formed after the exposure is developed by, for example, alkali development treatment to form a pattern. In the developing process, the photosensitive layer which is not irradiated with light in the exposure process is partially dissolved in the aqueous alkali solution to leave a portion irradiated with light.

The developer is preferably an organic base developer because it does not damage the underlying circuitry. The development temperature is usually from 20 ° C to 30 ° C, and the development time is from 20 to 240 seconds.

Using an aqueous alkali solution diluted with pure water as a developer to alkalize the organic The concentration of the compound is from 0.001% by mass to 10% by mass, and preferably from 0.01% by mass to 1% by mass. Examples of the organic base compound include ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, and 1,8-diazabicyclo ring. [5,4,0]-7-undecene. In the case where an aqueous alkali solution is used as the developer, it is usually washed (rinsed) with pure water after development.

In one embodiment, the preparation method of the second aspect of the present invention may optionally include a hardening process of hardening the pattern obtained after development by heating and/or exposure after the photosensitive layer forming process, the exposure process, and the developing process.

Second aspect solid state photographic element

A solid-state photographic element according to a second aspect of the present invention is a light-shielding film having a second aspect of the present invention on the other surface of a substrate having a photographic element unit on its surface.

That is, since the solid-state photographic element of the present invention has a light-shielding film formed using the black curable composition of the second aspect of the present invention, it is incident on the ruthenium substrate (solid state) from the surface opposite to the surface having the photographic element unit. The noise caused by infrared light on the basis of the photographic element or the noise caused by the residue is reduced.

The structure of the solid-state photographic element of the present invention is not particularly limited as long as the ruthenium substrate has a photographic element unit on one surface (specifically, the photographic element unit has a plurality of photographic elements such as a configuration in a matrix arrangement) and on the other surface The light-shielding film of the present invention may be used.

The photographic element can be CCD or CMOS.

There is a connection to an adhesive substrate (hereinafter, also referred to as "the surface" on the surface opposite to the surface on which the photographic element unit is formed, as disclosed in JP-A No. 2009-99591 or JP-A No. 2009-158863. The structure of the solid-state photographic element of the metal electrode of the circuit board") is suitable for the structure of the solid-state photographic element of the present invention.

In other words, a suitable embodiment of the solid state imaging element of the present invention is a solid state imaging element having: on one surface (referred to as the "first major surface" in some cases) Or "front side" a substrate having a photographic element unit; a metal electrode provided on the other surface of the ruthenium substrate (hereinafter, also referred to as "second main surface") and electrically connected to the photographic element unit; The light-shielding film of the present invention is patterned on a surface of a metal electrode having a tantalum substrate and patterned to expose at least a portion of the metal electrode.

First, a prior art solid-state photographic element using a wire bonding method is described for comparison with the above-described embodiments.

The prior art solid state imaging element is attached to the circuit board by wire bonding.

Specifically, the solid-state imaging element is placed on the circuit board, and the connection electrodes provided on the side of the photographic element unit of the 矽 substrate are connected to the connection electrodes on the circuit board by wires. In the structure using the wire bonding method, the area of the bonding region is increased and it is difficult to minimize the camera module.

Instead, the solid-state imaging element of one of the above embodiments is connected to an adhesive substrate (hereinafter, also referred to as a "circuit board") via a connecting material such as a solder ball instead of a wire.

The solid-state photographic element of one of the above embodiments is connected to the circuit board by: placing the solid-state photographic element and the circuit board in such a manner that the metal electrode and the connecting electrode on the circuit board are opposite to each other, and connecting via the connecting material The metal electrode is connected to the electrode (see, for example, Figures 9 and 10 described below).

A solid-state photographic element (without wires) as in one of the embodiments described above can be largely made to a large extent because the solid-state photographic element used is connected to the circuit board via a metal electrode on the other surface to save wire bonding space. The camera module is minimized (see, for example, "Toshiba Corporation New Release "About reinforcement of CMOS image sensor business by CMOS camera module internal development promotion for cellular phones" [online] October 1, 2007, [Search for November 12, 2009] ], Internet <URL: http://www.toshiba.co.jp/about/press/2007_10/prJ0102.htm>").

However, in the case where the solid-state photographic element used is connected to the circuit board via the metal electrode on the other side surface, due to the thickness of the metal electrode or the size of the connecting material (for example, the solder ball 260), between the solid-state photographic element and the circuit board A gap is easily generated, and infrared light is easily incident on the ruthenium substrate via the gap.

Similarly, for example, in the case of the camera module 200 as described below, it has a light-shielding property and an electronic shield 44. However, since the volume of the solder balls 260 is unbalanced, it is extremely difficult to completely shift in terms of processing accuracy. In addition to the light blocking property and the gap S between the electronic shield 244 and the circuit board 270.

For the reasons described above, the structure of a solid-state photographic element that is connected to a circuit board via a metal electrode on the other surface is highly desirable to block infrared light incident on the other surface of the substrate.

Therefore, in this structure, the effect of the present invention (improving the infrared light absorbing characteristics and reducing the noise caused by infrared light) is further exerted.

A solid-state photographic element having a metal electrode on the other surface has a structure in which a metal electrode needs to be connected to a circuit board via a connection material for connection.

Therefore, in this structure, the action of the present invention (reducing the residue and reducing the noise caused by the residue) is further exerted.

In one of the above embodiments, a coating such as a solder resist layer may be formed on the underlying layer of the metal electrode (away from one side of the ruthenium substrate) toward the underlying layer of the opaque film (near one side of the ruthenium substrate). Protect the insulation.

That is, one of the embodiments described above may have a form of forming a protective insulating layer provided on a second main surface on which a metal electrode is formed and patterned to expose at least a portion of the metal electrode, and the light-shielding film is covered and protected. The insulating layer is patterned and exposed to at least a portion of the metal electrode.

In one embodiment described above, the manner of "electrically connecting" is not limited to direct connection and includes indirect connection via peripheral circuitry.

Depending on the composition of the metal electrode or the like, the solder resist may be arbitrarily selected. The choice, but examples thereof include a solder resist containing the following thermosetting resin.

Examples of the thermosetting resin that can be used include a radical polymerizable resin having an unsaturated double bond, such as an epoxy resin, a phenol resin, a bis-maleimide resin, a cyanate resin, a diallyl phthalate An ester resin, an unsaturated polyester resin, a polyimide resin, a melamine resin, a urea resin, and an epoxy acrylate, and an epoxy resin is preferred. The resin constituting the solder resist may be used singly or in combination with an epoxy resin and other resins.

When the thermosetting resin contained in the solder resist contains an epoxy resin, the adhesion of the light-shielding film to the side surface (solder resist) of the substrate can be further improved as compared with the case where the solder resist does not contain an epoxy resin.

It is believed that the adhesion between the light-shielding film formed of the black curable composition and the solder resist is due to the strong acid group (such as a phosphate group or the (2B)) contained in the dispersible resin in the black curable composition. The sulfonic acid group is enhanced by ring-opening polymerization.

The content of the epoxy resin in the solder resist is preferably from 10% by mass to 80% by mass, and more preferably from 30% by mass to 60% by mass, from the viewpoint of further improving the adhesion.

Examples of the other components contained in the solder resist include well-known constituent materials such as a photopolymerization initiator, a sensitizer, or a colorant.

Hereinafter, although a specific example of one of the above embodiments is described with reference to FIGS. 9 and 10, the present invention is not limited to the following specific examples.

In Figures 9 and 10, the same reference numerals are used to indicate the parts.

In the description, "upper", "upper" and "upper" indicate the far side from the time of viewing of the substrate 110, and "lower", "lower" and "lower" indicate the side adjacent to the substrate 110.

Figure 9 is a schematic cross-sectional view illustrating the configuration of a camera module having solid state photographic elements associated with a particular example of one of the embodiments described above.

The camera module 200 shown in FIG. 9 is connected to a circuit board 270 as an adhesive substrate via a solder ball 260 as a connecting member.

In particular, the camera module 200 includes a solid-state photographic element substrate 100 having a photographic element unit on a first major surface of the sputum substrate; and a glass substrate 230 disposed on a first major surface side of the solid-state photographic element substrate 100 (transparent An infrared light-cut filter 242 disposed above the glass substrate 230; a lens holder 250 disposed above the glass substrate 230 and the infrared light-cut filter 242 and having a photographic lens 240 in the internal space; A light-shielding and electronic shield 244 disposed around the photographic element substrate 100 and the glass substrate 230. The members are adhered by the adhesives 221, 241, 243, and 245.

In the camera module 200, the external incident light h is sequentially transmitted through the photographic lens 240, the infrared cut filter 242, and the glass substrate 230, and then reaches the photographic element unit of the solid-state photographic element substrate 100.

The camera module 200 is connected to the circuit board 270 via a solder ball 260 (connection material) on the second main surface side of the solid-state imaging element substrate 100.

Fig. 10 is an enlarged cross-sectional view showing the solid-state imaging element substrate 100 of Fig. 9.

The solid-state imaging element substrate 100 includes a ruthenium substrate 110 (as a base), a photographic element 112, an interlayer insulating layer 113, a base layer 114, a red filter 115R, a green filter 115G, a blue filter 115B, and an overlying layer. 116, microlens 117, light-shielding film 118, insulating layer 122, metal electrode 123, solder resist layer 124, internal electrode 126, and element surface electrode 127.

However, the solder resist layer 124 can be omitted.

First, the configuration of the first main surface of the solid-state imaging element substrate 100 is mainly described.

As shown in FIG. 10, a plurality of photographic elements 112 (such as CCD or CMOS) are photographic element units disposed in two dimensions on a first major surface of the ruthenium substrate 110 which is the base of the solid state photographic element substrate 100.

On the photographic element 112 in the photographic element unit, an interlayer insulating layer 113 is formed, and a foundation layer 114 is formed on the interlayer insulating layer 113. Further, a red color filter 115R, a green color filter 115G, and a blue color filter 115B (hereinafter, in some cases) Hereinafter, collectively referred to as "color filter 115", respectively, are disposed on the base layer 114 to correspond to the photographic element 112.

A light-shielding film (not shown) may be provided at the boundary between the red color filter 115R, the green color filter 115G, and the blue color filter 115B and the periphery of the photographic element unit. This light-shielding film can be made of, for example, a well-known black resist.

An over cladding layer 116 is formed on the color filter 115, and a microlens 117 is formed on the over cladding layer 116 to correspond to the photographic element 112 (color filter 115).

Further, peripheral circuits (not shown) and internal electrodes 126 are provided on the first main surface at the periphery of the photographic element unit, and the internal electrodes 126 are connected to the photographic elements 112 via peripheral circuits.

The element surface electrode 127 is formed on the internal electrode 126 via the interlayer insulating layer 113. In the interlayer insulating layer 113 interposed between the internal electrode 126 and the element surface electrode 127, contact plugs (not shown) electrically connecting them to each other are formed. The element surface electrode 127 is for applying a voltage or reading a signal via the contact plug and the internal electrode 126.

A foundation layer 114 is formed on the element surface electrode 127. An overlying layer 116 is formed on the base layer 114. The base layer 114 and the overlying layer 116 formed on the surface electrode 127 of the element have openings to form pad holes exposing a portion of the surface electrode 127 of the element.

The configuration of the first major surface side of the solid state imaging element substrate 100 is described above.

In the first main surface side of the solid-state imaging element substrate 100, an adhesive 221 is provided in the vicinity of the photographic element unit, and the solid-state photographic element substrate 100 is adhered to the glass substrate 230 via the adhesive 221 .

The germanium substrate 110 has a through hole penetrating the germanium substrate 110, and a penetrating electrode as a part of the metal electrode 123 is disposed in the through hole. The photographic element unit is electrically connected to the circuit board 270 via a penetrating electrode.

Subsequently, the configuration of the second main surface side of the solid-state photographic element substrate 100 is mainly described.

On the second major surface side, the insulating layer 122 is formed from the second major surface via the inner wall of the via.

On the insulating layer 122, a patterned metal electrode 123 is provided from a region on the second major surface of the germanium substrate 110 to the inside of the via. The metal electrode 123 is an electrode for connecting the photographic element unit of the solid-state photographic element substrate 100 to the circuit board 270.

The penetrating electrode is a portion of the metal electrode 123 formed inside the through hole. The through electrode penetrates the germanium substrate 110 and a portion of the interlayer insulating layer, reaches the lower side of the inner electrode 126, and is electrically connected to the inner electrode 126.

Further, on the side of the second main surface, a solder resist layer 124 (protective insulating layer) covering the second main surface on which the metal electrode 123 is formed is provided, and having a hole exposing a part of the metal electrode 123.

Further, on the side of the second main surface, a light-shielding film 118 covering the second main surface on which the solder resist layer 124 is formed is provided, and having a hole exposing a part of the metal electrode 123.

As the light-shielding film 118, the above-described light-shielding film of the present invention is used.

Thereby, infrared light incident on the ruthenium substrate 110 from the second main surface side (the other surface side) can be blocked. Also, in the hole of the light-shielding film 118 (the portion where the metal electrode 123 is exposed), the development residue is suppressed. For the reason described, a good connection between the metal electrode 123 and the solder ball 260 is maintained, and a good connection between the photographic element unit constituted by the photographic element 112 and the circuit board 270 is further maintained.

Further, the adhesion of the light-shielding film 118 to the side surface of the ruthenium substrate 110 is improved.

In FIG. 10, although the light-shielding film 118 is patterned to cover a portion of the metal electrode 123 and expose the remaining portion, it may be patterned to expose the entire metal electrode 123 (as for the patterning of the solder resist layer 124) .

Further, the solder resist layer 124 may be omitted, and the light-shielding film 118 may be directly formed on the second main surface on which the metal electrode 123 is formed.

The solder ball 260 is provided as a connecting member on the exposed metal electrode 123, and the metal electrode 123 of the solid-state imaging element substrate 100 is electrically connected to a connection electrode (not shown) of the circuit board 270 via the solder ball 260.

In this manner, although the configuration of the solid-state photographic element substrate 100 is described, it can be by a well-known method such as the method disclosed in paragraphs [0033] to [0068] of JP-A No. 2009-158863 or The method disclosed in paragraphs 0036 to 0065 of JP-A No. 2009-99591) forms parts other than the light-shielding film 118 in the solid-state imaging element substrate 100.

The light-shielding film 118 can be formed according to the method for producing a light-shielding film of the present invention.

The interlayer insulating layer 113 is formed in the form of a SiO ₂ layer or a SiN layer by, for example, sputtering, CVD (Chemical Vapor Deposition) or the like.

The color filter 115 is formed by photolithography using, for example, a well-known color resist.

The overcoat layer 116 and the base layer 114 are formed by photolithography using, for example, a resist well known for forming an interlayer organic layer.

The microlens 117 is formed by photolithography using, for example, a styrene-based resin or the like.

The solder resist layer 124 is formed by photolithography using, for example, a well-known solder resist such as a phenol-based resin, a polyimide-based resin, or an amine-based resin.

The solder ball 260 is formed using Sn-Ag, Sn-Cu, Sn-Ag-Cu or the like in the form of, for example, Sn-Pb (co-crystal), 95 Pb-Sn (high-lead high-melting solder), and no Pb solder. . The solder balls 260 are formed in a spherical shape such as a diameter of 100 μm to 1000 μm (preferably, a diameter of 150 μm to 700 μm).

The internal electrode 126 and the component surface electrode 127 are formed by a metal electrode of Cu or the like by, for example, CMP (Chemical Mechanical Polishing) or photolithography and etching.

The metal electrode 123 is made of, for example, sputtering, photolithography, etching, or electrolytic plating, and is composed of Cu, Au, Al, Ni, W, Pt, Mo, Cu compound, W compound, Mo. A metal electrode form made of a compound or the like is formed. The metal electrode 123 may be formed as a single layer or as a multilayer including two or more layers.

The film thickness of the metal electrode 123 is, for example, 0.1 μm to 20 μm (preferably 0.1 μm to 10 μm). The ruthenium substrate 110 is not particularly limited, and a ruthenium substrate thinned by peeling off the other surface may be used. The thickness of the substrate is not limited, and may be a germanium wafer having a thickness of, for example, 20 μm to 200 μm, preferably 30 to 150 μm.

The via holes of the germanium substrate 110 are formed by, for example, photolithography and RIE (reactive ion etching).

As described above, although the solid-state imaging element substrate 100 as a specific example of an embodiment has been described with reference to FIGS. 9 and 10, one embodiment described above is not limited to the forms in FIGS. 9 and 10, and the configuration is It is not particularly limited as long as it is configured to have a metal electrode and a light-shielding film on the side of the other surface.

Light-shielding color filter for solid-state photographic element in the third aspect and preparation method thereof

Subsequently, a light-shielding color filter for a solid-state photographic element according to a third aspect of the present invention and a method of producing the same will be described.

The light-shielding color filter for solid-state photographic elements of the present invention has a pattern obtained by using the black curable composition of the present invention.

The method for producing a light-shielding color filter for a solid-state photographic element of the present invention comprises a process of applying a black curable composition of the present invention onto a support, followed by exposure through a mask and development to form a pattern.

Specifically, the preparation method comprises: applying the above-described black curable composition of the third aspect of the present invention to a support to form a black curable composition layer (hereinafter, appropriately referred to as "black curable composition" a layer forming process"); exposing a black curable composition layer through a mask (hereinafter, appropriately referred to as "exposure process"); and developing a black curable composition layer after exposure to form a pattern (hereinafter, Properly referred to as "development process").

More specifically, the black curable composition of the third aspect of the present invention is applied to the support (substrate) directly or via another layer to form a black curable composition layer (that is, a black curable composition layer is formed). Process); using a predetermined mask pattern to partially cure only the light-irradiated black curable composition (ie, an exposure process); and using a developer for development (ie, a development process) to form a pattern formed by black pixels A film for producing a light-shielding color filter for a solid-state photographic element according to a third aspect of the present invention.

Hereinafter, each process in the method of producing a light-shielding color filter for a solid-state photographic element of the present invention will be described.

[Black hardening composition layer forming process]

In the black curable composition layer forming process, the black curable composition of the present invention is applied onto a support to form a black curable composition layer.

Examples of the support used in the process include soda glass for liquid crystal display, alkali-free glass, Pyrex (registered trademark) glass, quartz glass, and glass obtained by adhering a transparent conductive film, or for solid-state photographic elements or A photoelectric conversion element substrate including a similar example of a germanium substrate or the like, and a complementary metal oxide semiconductor (CMOS).

An underlying layer may be provided in the support as appropriate to achieve improved adhesion to the overlying layer, prevention of material diffusion, or planarization of the substrate surface.

As a method of applying the black curable composition of the present invention to a support, various coating methods such as a slit coating method, a spray coating method, an inkjet method, a spin coating method, a cast coating method, a roll coating method, and the like can be used. Screen printing method or the like.

The coating thickness of the black curable composition after drying is preferably from 0.35 μm to 1.5 μm, and more preferably from 0.40 μm to 1.0 μm, from the viewpoint of resolution and developability.

The black curable composition coated on the support is usually dried at a temperature of from 70 ° C to 110 ° C for 2 minutes to 4 minutes, and then a black curable composition layer is formed.

[Exposure Process]

In the exposure process, a black curable composition layer formed in the black curable composition layer forming process is exposed using a mask, and then only the coated portion irradiated with light is hardened using a predetermined mask pattern.

Preferably, the exposure is performed by radiation, and as the radiation used during the exposure, in particular, ultraviolet rays such as g rays, h rays or i rays are preferably used, and among them, i rays are preferable, and lithography is better. For the i-ray stepper. The irradiation intensity is 5 mJ/cm 2 to 1500 mJ/cm 2 , more preferably 10 mJ/cm 2 to 1000 mJ/cm 2 , and most preferably 10 mJ/cm 2 to 800 mJ/square Centimeters.

[development process]

After the exposure process, the black curable composition layer is developed after exposure by alkali development treatment (development treatment), and a portion thereof which is not irradiated with light in the exposure process is dissolved in the aqueous alkali solution. Thereby, only the light hardened portion is retained.

The developer is preferably an organic base developer because it does not damage the underlying circuitry. The development temperature is usually from 20 ° C to 30 ° C, and the development time is from 20 to 90 seconds.

The aqueous alkali solution diluted with pure water is used as the developer so that the concentration of the organic base compound is from 0.001% by mass to 10% by mass, and preferably from 0.01% by mass to 1% by mass. Examples of the organic base compound include ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, and 1,8-diazabicyclo ring. [5,4,0]-7-undecene. In the case where an aqueous alkali solution is used as the developer, it is usually washed (rinsed) with pure water after development.

Further, an inorganic base can be used in the developer. Preferred examples of the inorganic base include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium citrate, sodium metasilicate, and the like.

In one embodiment, the preparation method of the third aspect of the present invention may optionally include hardening the pattern formed by heating and/or exposure after the black curable composition layer forming process, the exposure process, and the developing process. Hardening process.

The light-shielding color filter for solid-state photographic elements of the present invention can be produced by the black curable composition layer forming process, the exposure process, and the development (and the hardening process as the case may be) as described above.

Further, in the black curable composition layer forming process, the (A) inorganic pigment in the black curable composition can be changed to a coloring agent having a desired color (for example, a pigment or dye having a color), and thus color The curable composition can form a color curable composition layer corresponding to RGB (hereinafter, referred to as "color hardenable composition layer forming process").

Thus, for example, in the light-shielding color filter for solid-state photographic elements obtained as described above, the color hardening composition layer forming process, the exposure process, and the developing process are repeated (in addition, hardening as the case may be) The process) is to obtain a large number of desired colors, and thereby form a color filter having a color pattern of a desired color.

[The third aspect of the solid-state photographic element]

The solid-state photographic element of the present invention has the opaque color filter for solid-state photographic elements of the present invention. Since the light-shielding color filter for solid-state photographic elements of the present invention uses the black curable composition of the present invention, the formed pattern exhibits high adhesion to the support and excellent resistance due to the hardened black curable composition. The developability is good, so that the exposure sensitivity is good, and thus the adhesion of the exposed portion to the substrate is good, and a high-resolution pattern that provides a desired cross-sectional shape can be formed. Therefore, solid-state imaging elements are suitable for high-resolution CCD elements or CMOS or similar components with a resolution of more than one million pixels.

The light-shielding color filter for solid-state photographic elements of the present invention can be used, for example, as a light-shielding color filter for solid-state photographic elements disposed between a photosensitive unit constituting each pixel of a CCD and a microlens for collecting light. Light film.

The black curable composition of the third aspect of the present invention can be used to manufacture a solid-state photographic element. Specifically, in a substrate having one surface (this surface is also referred to as "first major surface") and the other surface (this surface is also referred to as "second main surface"), the photographic element unit is formed on one surface Upper, and the infrared-shielding film is formed on the other surface In this case, the black curable composition of the present invention can be used to form an infrared ray blocking film. Further, the black curable composition of the present invention can be used for producing a light-shielding color filter which is formed at a desired position on the first main surface of the photographic element unit on which the solid-state photographic element is formed and which has a function of blocking unintentional light. Light film.

In the following, the embodiments are described.

Third aspect solid state photographic element

A solid-state photographic element according to a third aspect of the present invention is characterized in that the other surface of the ruthenium substrate having the photographic element unit on one surface has the illuminating film of the third aspect of the invention.

That is, since the solid-state imaging element of the present invention has an infrared-shielding film formed using the photosensitive resin composition of the third aspect of the present invention, it is incident on the ruthenium substrate from the surface opposite to the surface having the photographic element unit. The noise caused by infrared light or the noise caused by the residue on the base of the solid-state photographic element is reduced.

The structure of the solid-state photographic element of the third aspect of the present invention is not particularly limited as long as the ruthenium substrate has a photographic element unit on one surface (specifically, the photographic element unit has a plurality of photographic elements in a configuration such as a matrix arrangement) Further, on the other surface, the infrared ray film of the third aspect of the invention may be used.

The photographic element can be CCD or CMOS.

In the above, as disclosed in JP-A No. 2009-99591 or JP-A No. 2009-158863, there is a surface for connection to an adhesive substrate on a surface opposite to a surface on which a photographic element unit is formed (hereinafter, also referred to as The structure of the solid-state photographic element of the metal electrode as the "circuit board" is suitable for the structure of the solid-state photographic element of the third aspect of the present invention.

In other words, a suitable embodiment of the solid-state photographic element of the third aspect of the invention is a solid-state photographic element having photographic elements on a surface (referred to as "first major surface" or "front" in some cases) a germanium substrate; a metal electrode provided on the other surface of the germanium substrate (hereinafter, also referred to as a "second main surface") and electrically connected to the photographic element unit; and a surface provided on the metal electrode having the germanium substrate a fourth aspect of the invention that is patterned to expose at least a portion of the metal electrode Photo film.

First, a prior art solid-state photographic element using a wire bonding method is described for comparison with the above-described embodiments.

Prior art solid state photographic elements are connected to the board by wire bonding.

Specifically, the solid-state imaging element is placed on the circuit board, and the connection electrodes provided on the side of the photographic element unit of the 矽 substrate are connected to the connection electrodes on the circuit board by wires. In the structure using the wire bonding method, the area of the bonding region is increased and it is difficult to minimize the camera module.

In contrast, the solid-state imaging element of one of the above embodiments is connected to an adhesive substrate (hereinafter, also referred to as a "circuit board") via a connecting material such as a solder ball instead of a wire.

The solid-state photographic element of one of the above embodiments is connected to the circuit board by: placing the solid-state photographic element and the circuit board in such a manner that the metal electrode and the connecting electrode on the circuit board are opposite to each other, and the connecting material is The metal electrode is connected to the connection electrode (see, for example, Figures 9 and 10 described below).

A solid-state photographic element (without wires) as in one of the embodiments described above can be largely made to a large extent because the solid-state photographic element used is connected to the circuit board via a metal electrode on the other surface to save wire bonding space. The camera module is minimized (see, for example, "Toshiba Corporation New Release "About reinforcement of CMOS image sensor business by CMOS camera module internal development promotion for cellular phones").

However, in the case where the solid-state photographic element used is connected to the circuit board via the metal electrode on the other surface side, due to the thickness of the metal electrode or the size of the connecting material (for example, the solder ball 260), between the solid-state photographic element and the circuit board A gap is easily generated, and infrared light is easily incident on the ruthenium substrate via the gap.

In addition, for example, in the case of the camera module 200 as described below, it has a light-shielding and electronic shield 44, but due to the imbalance of the solder balls 260, In terms of processing accuracy, it is extremely difficult to completely remove the gap S between the light shielding and electronic shield 244 and the circuit board 270.

For the reasons described above, the structure of a solid-state photographic element that is connected to a circuit board via a metal electrode on the other surface is highly desirable to block infrared light incident on the other surface of the substrate.

Therefore, in the above structure, the action of the present invention (improving the infrared light absorbing characteristics and reducing the noise caused by infrared light) is further exerted.

A solid-state photographic element having a metal electrode on the other surface has a structure in which a metal electrode needs to be connected to a circuit board via a connection material for connection.

Therefore, in the structure, the action of the present invention (reducing the residue and reducing the noise caused by the residue) is further exerted.

In one of the embodiments described above, a solder resist layer (near one side of the ruthenium substrate) may be formed on the metal electrode over the cladding layer (away from one side of the ruthenium substrate) such as solder resist. Protective insulation layer of the layer.

That is, one of the embodiments described above may have a form of forming a protective insulating layer provided on a second main surface on which a metal electrode is formed and patterned to expose at least a portion of the metal electrode, and shielding the infrared light film The protective insulating layer is covered and patterned to expose at least a portion of the metal electrode.

In one embodiment described above, the manner of "electrically connecting" is not limited to direct connection and includes indirect connection via peripheral circuitry.

Hereinafter, although specific examples of one embodiment described above have been described with reference to FIGS. 9 and 10, the present invention is not limited to the following specific examples.

Figure 9 is a schematic cross-sectional view illustrating the configuration of a camera module having solid state photographic elements associated with a particular example of one of the embodiments described above.

Fig. 10 is an enlarged cross-sectional view showing the solid-state imaging element substrate 100 of Fig. 9.

In Figures 9 and 10, the same reference numerals are used to indicate the parts.

In the description, "upper", "upper" and "upper side" indicate the far side when viewed from the substrate 110, and "lower", "lower" and "lower" indicate the side closer to the 矽 substrate 110.

The camera module 200 shown in FIG. 9 is connected to a circuit board 270 as an adhesive substrate via a solder ball 260 as a connecting member.

In particular, the camera module 200 includes a solid-state photographic element substrate 100 having a photographic element unit on a first major surface of the sputum substrate; and a glass substrate 230 disposed on a first major surface side of the solid-state photographic element substrate 100 (transparent An infrared light-cut filter 242 disposed above the glass substrate 230; a lens holder 250 disposed above the glass substrate 230 and the infrared light-cut filter 242 and having a photographic lens 240 in the internal space; A light-shielding and electronic shield 244 disposed around the photographic element substrate 100 and the glass substrate 230. The members are adhered by the adhesives 221, 241, 243, and 245.

In the camera module 200, the external incident light h is sequentially transmitted through the photographic lens 240, the infrared cut filter 242, and the glass substrate 230, and then reaches the photographic element unit of the solid-state photographic element substrate 100.

The camera module 200 is connected to the circuit board 270 via a solder ball 260 (connection material) on the second main surface side of the solid-state imaging element substrate 100.

As shown in FIG. 10, the solid-state imaging element substrate 100 includes a ruthenium substrate 110 (as a base), a photographic element 112 formed on a first major surface of the ruthenium substrate 110, an interlayer insulating layer 113, a base layer 114, and a red filter. The sheet 115R, the green filter 115G, the blue filter 115B, the overlying layer 116, the microlens 117, the internal electrode 126, and the component surface electrode 127, and the insulating layer 122 formed on the second main surface of the 矽 substrate 110 The metal electrode 123, the solder resist layer 124, and the infrared ray blocking film 118. The internal electrode 126 and the metal electrode 123 are electrically connected at a portion where the through hole 110H connecting the first main surface and the second main surface is provided.

However, the solder resist layer 124 can be omitted.

First, the first main surface of the solid-state imaging element substrate 100 is mainly described. Configuration.

As shown in FIG. 10, a plurality of photographic elements 112 (such as CCD or CMOS) are photographic element units disposed in two dimensions on a first major surface of the ruthenium substrate 110 which is the base of the solid state photographic element substrate 100.

On the photographic element 112 in the photographic element unit, an interlayer insulating layer 113 is formed, and a foundation layer 114 is formed on the interlayer insulating layer 113. Further, a red color filter 115R, a green color filter 115G, and a blue color filter 115b (hereinafter, collectively referred to as "color filter 115" in some cases) are respectively disposed on the base layer 114 to correspond to Photography element 112.

A light-shielding film (not shown) may be provided at the boundary between the red color filter 115R, the green color filter 115G, and the blue color filter 115B and the periphery of the photographic element unit. The light-shielding film can be made of, for example, a well-known black resist.

An over cladding layer 116 is formed on the color filter 115, and a microlens 117 is formed on the over cladding layer 116 to correspond to the photographic element 112 (color filter 115).

Further, peripheral circuits (not shown) and internal electrodes 126 are provided at the periphery of the photographic element unit on the first main surface, and the internal electrodes 126 are connected to the photographic elements 112 via peripheral circuits.

The element surface electrode 127 is formed on the internal electrode 126 via the interlayer insulating layer 113. In the interlayer insulating layer 113 interposed between the internal electrode 126 and the element surface electrode 127, contact plugs (not shown) electrically connecting them to each other are formed. The element surface electrode 127 is for applying a voltage or reading a signal via the contact plug and the internal electrode 126.

A foundation layer 114 is formed on the element surface electrode 127. An overlying layer 116 is formed on the base layer 114. The base layer 114 and the overlying layer 116 formed on the surface electrode 127 of the element have openings to form pad holes exposing a portion of the surface electrode 127 of the component.

The configuration of the first major surface side of the solid state imaging element substrate 100 is described above.

Adhesive in the first main surface side of the solid-state imaging element substrate 100 The agent 221 is provided in the vicinity of the photographic element unit, and the solid-state photographic element substrate 100 is adhered to the glass substrate 230 via the adhesive 221.

The germanium substrate 110 has a through hole penetrating the germanium substrate 110, and a penetrating electrode as a part of the metal electrode 123 is disposed in the through hole. The photographic element unit is electrically connected to the circuit board 270 via a penetrating electrode.

Subsequently, the configuration of the second main surface side of the solid-state photographic element substrate 100 will be described.

On the second main surface of the ruthenium substrate 110, an insulating layer 122 is formed from the first main surface via the inner wall of the via hole 110H.

On the insulating layer 122, a patterned metal electrode 123 is provided from a region on the second main surface of the germanium substrate 110 to the inside of the via hole 110H. The metal electrode 123 is an electrode for connecting the photographic element unit of the solid-state photographic element substrate 100 to the circuit board 270.

The penetrating electrode is a portion of the metal electrode 123 formed inside the through hole 110H. The through electrode penetrates the germanium substrate 110 and a portion of the interlayer insulating layer, reaches the lower side of the inner electrode 126, and is electrically connected to the inner electrode 126.

Further, on the second main surface, a solder resist layer 124 (protective insulating layer) covering the second main surface on which the metal electrode 123 is formed and having the hole 124H exposing the portion 123E of the metal electrode 123 is provided.

Further, an infrared ray blocking film 118 covering the solder resist layer 124 other than the holes 124H is provided over the solder resist layer 124.

The infrared ray shielding film 118 is formed by lithography using the black curable composition of the present invention.

Thereby, infrared light incident on the ruthenium substrate 110 from the side of the second main surface is blocked. Further, the development residue in the metal electrode 123 is suppressed. For the reason described, a good connection between the exposed portion 123E of the metal electrode 123 and the solder ball 260 is maintained, and a good connection between the photographic element unit constituted by the photographic element 112 and the circuit board 270 is further maintained.

In FIG. 10, although the infrared ray blocking film 118 is patterned to cover a portion of the metal electrode 123 other than the exposed portion 123E, it may be patterned to expose the entire metal electrode 123 (for the patterning of the solder resist layer 124) The same is true.)

Further, the solder resist layer 124 may be omitted, and the infrared ray blocking film 118 may be formed directly over the metal electrode 123 to be in contact with the metal electrode 123.

The solder ball 260 is provided as a connection member on the exposed portion 123E of the metal electrode 123, and the metal electrode 123 of the solid-state imaging element substrate 100 is electrically connected to the connection electrode (not shown) of the circuit board 270 via the solder ball 260.

In this manner, although the configuration of the solid-state photographic element substrate 100 is described, it can be by a well-known method such as the method disclosed in paragraphs [0033] to [0068] of JP-A No. 2009-158863 or The method disclosed in paragraphs 0036 to 0065 of JP-A No. 2009-99591) forms parts other than the light-shielding film 118 in the solid-state imaging element substrate 100.

The infrared ray blocking film 118 can be formed according to the method for producing an infrared ray shielding film of the present invention.

The interlayer insulating layer 113 is formed in the form of a SiO ₂ layer or a SiN layer by, for example, sputtering, CVD (Chemical Vapor Deposition) or the like.

The color filter 115 is formed by photolithography using, for example, a well-known color resist.

The overcoat layer 116 and the base layer 114 are formed by photolithography using, for example, a resist well known for forming an interlayer organic layer.

The microlens 117 is formed by photolithography using, for example, a styrene-based resin or the like.

The solder resist layer 124 is formed by photolithography using, for example, a well-known solder resist such as a phenol-based resin, a polyimide-based resin, or an amine-based resin.

The solder ball 260 is made of Sn-Ag, Sn-Cu, Sn-Ag-Cu or the like, for example, Sn-Pb (eutectic), 95 Pb-Sn (high-lead high-melting solder), and no Pb solder. Formed. The solder balls 260 are formed in a spherical shape such as a diameter of 100 μm to 1000 μm (preferably, a diameter of 150 μm to 700 μm).

The internal electrode 126 and the component surface electrode 127 are formed by a metal electrode of Cu or the like by, for example, CMP (Chemical Mechanical Polishing) or photolithography and etching.

The metal electrode 123 is a metal electrode made of, for example, sputtering, photolithography, etching, or electrolytic plating, with Cu, Au, Al, Ni, W, Pt, Mo, Cu compound, W compound, Mo compound, or the like. Form formation. The metal electrode 123 may be formed as a single layer or as a multilayer including two or more layers.

The film thickness of the metal electrode 123 is, for example, 0.1 μm to 20 μm (preferably 0.1 μm to 10 μm).

The germanium substrate may be a germanium wafer having a thickness of, for example, 10 micrometers to 10,000 micrometers (preferably 100 to 1,000 micrometers).

The via holes of the germanium substrate 10 are formed by, for example, photolithography and RIE (reactive ion etching).

As described above, although the solid-state imaging element substrate 100 as a specific example of an embodiment has been described with reference to FIGS. 9 and 10, one embodiment described above is not limited to the forms in FIGS. 9 and 10, and the configuration is It is not particularly limited as long as it is configured to have a metal electrode and a light-shielding film on the side of the other surface.

The third aspect of the infrared light shielding film

An infrared ray blocking film is formed on the second major surface of the ruthenium substrate as described above.

For the reasons described above, the infrared-shielding film of the present invention has excellent infrared light blocking characteristics.

Further, the residue at the vicinity of the infrared ray shielding film of the present invention (the region on the ruthenium substrate where the infrared ray shielding film is not formed) is reduced.

The film thickness of the infrared ray blocking film is not particularly limited, and is preferably from 0.1 μm to 10 μm, more preferably 0.3 μm from the viewpoint of effectively achieving the effect of the present invention. Up to 5.0 microns, and most preferably from 0.5 microns to 3.0 microns. The pattern size of the infrared ray-blocking film is not particularly limited, and is preferably 1000 μm or less, more preferably 500 μm or less, and most preferably 300 μm or less from the viewpoint of effectively achieving the action of the present invention. The lower limit is preferably 1 micrometer.

The spectral characteristics of the light-shielding film of the present invention are not particularly limited in view of further improving the infrared light-shielding property, the light-shielding property of the visible light region, and the light-shielding property of the infrared region, and the like, but the wavelength of 365 nm is 365 nm. The ratio of the optical density (OD ₃₆₅ ) to the optical density (OD ₁₂₀₀ ) at a wavelength of 1200 nm [OD ₁₂₀₀ / OD ₃₆₅ ] is preferably 0.5 to 3.

The optical density (OD) was obtained as an OD value by using the UV-3600 measurement manufactured by Shimadzu Corporation to measure the transmittance of the film, and using the following equation B to convert the obtained transmittance (%T).

OD value = -Log(%T/100) Equation B

In the third aspect of the invention, the optical density at a wavelength of λ nm is represented by "OD _λ ".

From the viewpoint of further improving the balance between the infrared ray shielding property, the light shielding property of the visible light region, and the light shielding property of the infrared region, the optical density of the light shielding film satisfies the following conditions from the viewpoint of effectively achieving the action of the present invention. That is: the ratio [OD ₁₂₀₀ / OD ₃₆₅ ] is preferably from 1.0 to 2.5 and most preferably from 1.3 to 2.0.

The optical density [OD ₁₂₀₀ ] of the light-shielding film at a wavelength of 1200 nm is preferably from 1.5 to 10, and more preferably from 2 to 10.

The optical density (OD ₃₆₅ ) of the light-shielding film at a wavelength of 365 nm is preferably from 1 to 7, and more preferably from 2 to 6.

The optical density of the light-shielding film in the wavelength range of from 900 nm to 1300 nm is preferably from 2 to 10, more preferably from 2 to 9, and most preferably from 2 to 8.

The ratio of the light-shielding film [OD ₉₀₀ / OD ₃₆₅ ] is preferably from 1.0 to 2.5, and more preferably from 1.1 to 2.5.

The ratio of the light-shielding film [OD ₁₁₀₀ / OD ₃₆₅ ] is preferably from 0.6 to 2.5, and more preferably from 0.7 to 2.5.

The ratio of the light-shielding film [OD ₁₃₀₀ /OD ₃₆₅ ] is preferably from 0.4 to 2.3, and more preferably from 0.5 to 2.0.

The above-described detailed example of the infrared ray-blocking film according to the third aspect of the present invention comprises a titanium black dispersion liquid and an infrared ray blocking film according to the application of the photosensitive resin composition of the third aspect of the invention.

Method for preparing masking infrared light film of third aspect

The light-shielding film of the third aspect of the present invention is produced by applying the above-described black curable composition of the third aspect of the present invention to the second main surface of the substrate having the photographic element unit on the first main surface Forming a photosensitive layer (hereinafter, also referred to as "photosensitive layer forming process"); patterning the photosensitive layer (hereinafter, also referred to as "exposure process"); and developing the photosensitive layer after exposure to form a pattern ( Hereinafter, it is also referred to as "developing process").

According to the method of producing the light-shielding film of the third aspect of the present invention, the residue in the region other than the region where the light-shielding film is formed can be reduced during the formation of the light-shielding film (hereinafter, also referred to as "developing residue" "), because the light-shielding film has excellent infrared light-shielding properties.

Hereinafter, each process in the method of producing the light-shielding color filter of the present invention will be described.

Photosensitive layer forming process

In the photosensitive layer forming layer, an organic solvent solution (hereinafter, simply referred to as "coating liquid") of the black curable composition of the present invention is applied onto a ruthenium substrate to remove an organic solvent, thereby forming a photosensitive layer. During the removal of the organic solvent, consideration may be given to ways to help remove the organic solvent, such as blowing hot air.

Examples of the method of applying the coating liquid onto the ruthenium substrate include various coating methods such as a slit coating method, an inkjet method, a spin coating method, a cast coating method, a roll coating method, or a screen printing method.

The coating film thickness (dry film thickness) of the black curable composition is preferably from 0.35 μm to 3.0 μm, and more preferably from 0.50 μm to 2.5 μm, from the viewpoint of resolution and developability.

The photosensitive resin composition coated on the ruthenium substrate is usually dried at a temperature of from 70 ° C to 130 ° C for 2 minutes to 4 minutes, and thereby a photosensitive layer is formed.

Exposure process

In the exposure process, a photosensitive layer formed in the photosensitive layer forming process is subjected to pattern exposure using, for example, a mask. When the exposure is performed using a mask, the light-irradiated coating film is partially hardened.

The exposure is preferably performed by irradiation with radiation, and as the radiation for exposure, ultraviolet rays such as g rays, h rays or i rays are preferably used, and high pressure mercury or the like is more preferably used. The irradiation intensity is 5 mJ to 3,000 mJ, more preferably 10 mJ to 2,000 mJ, and most preferably 10 mJ to 1000 mJ.

Developing process

After the exposure process, the photosensitive layer formed after the exposure is developed by, for example, alkali development treatment to form a pattern. In the developing process, the photosensitive layer which is not irradiated with light in the exposure process is partially dissolved in the aqueous alkali solution to leave a portion irradiated with light.

The developer is preferably an organic base developer because it does not damage the underlying circuitry. The development temperature is usually from 20 ° C to 30 ° C, and the development time is from 20 to 240 seconds.

The aqueous alkali solution diluted with pure water is used as the developer so that the concentration of the organic base compound is from 0.001% by mass to 10% by mass, and preferably from 0.01% by mass to 1% by mass. Examples of the organic base compound include ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, and 1,8-diazabicyclo ring. [5,4,0]-7-undecene. In the case where an aqueous alkali solution is used as the developer, it is usually washed (rinsed) with pure water after development.

In one embodiment, the preparation method of the third aspect of the present invention may optionally include a hardening process of hardening the pattern obtained after development by heating and/or exposure after the photosensitive layer forming process, the exposure process, and the developing process.

"Light-shielding color filter"

The black curable composition of the third aspect of the present invention can be used for producing a light-shielding color filter formed on a first main surface of a photographic element unit on which a solid-state photographic element has been formed. It has the desired position and has the function of blocking the light that is inadvertently entered. The light-shielding color filter is manufactured in the same manner as the method of manufacturing an infrared-shielding film, and thus the description thereof is omitted.

Instance

Hereinafter, the present invention will be described in detail with respect to specific examples, but the invention is not limited to the examples. Unless otherwise specified, "parts" are by mass and "room temperature" means 25 °C.

First instance

[Synthesis Example 1-1: Synthetic Resin (1-1)]

The resin (1-1) which is the specific resin of the (B1) of the first aspect of the present invention is synthesized by using the phosphate group-containing monomer (1-1) and the macromonomer (1-1) according to the following scheme.

Next, 30 g (0.143 mol) of monomer (1-1) (PHOSMER M (trade name), manufactured by Unichemical Co., Ltd.), 70 g (0.047 mol, weight average molecular weight (in terms of polystyrene) (by means of GPC): 3,100) of the macromonomer (1-1) was added to 233 g of 1-methoxy-2-propanol, followed by heating at 80 ° C under a nitrogen/air stream . Next, 1.54 g (7.6 mmol) of dodecanethiol and 0.5 g of dimethyl 2,2'-azobisisobutyrate (V-601 (trade name), by Wako Pure Chemical Industries, were added thereto. (manufactured by Ltd.), followed by stirring for 2 hours. Then, add to it 0.5 g of dimethyl 2,2'-azobisisobutyrate (V-601 (trade name), manufactured by Wako Pure Chemical Industries, Ltd.) was added, followed by stirring for 2 hours. Next, 0.5 g of dimethyl 2,2'-azobisisobutyrate (V-601, manufactured by Wako Pure Chemical Industries, Ltd.) was added thereto, followed by raising the temperature to 90 ° C and stirring for 2 hours. Thus, a 30% by mass solution of the resin (1-1) in 1-methoxy-2-propanol was obtained.

The resin (1-1) had a weight average molecular weight of 25,000 (measured by means of GPC measurement), a number average molecular weight of 11,000, and an acid value of 150 mg KOH/g.

[Synthesis Examples 1-2 to 1-9: Synthetic Resins (1-2) to (1-9)]

Resins (1-2) to (1-9) were obtained in the same manner as in Synthesis Example 1-1 except that the monomers and macromonomers shown in Table 1 were used. The weight average molecular weight, number average molecular weight, and acid value of the obtained resin are shown in Table 1.

[Synthesis Example 1-10: Synthetic Resin (1-10)]

The resin (1-10) which is the (B1) specific resin of the third aspect of the present invention is synthesized by using the phosphoric acid group-containing monomer (1-5) and the macromonomer (1-3) according to the following scheme.

Next, 30 g (0.143 mol) of monomer (1-5) (manufactured by Tokyo Chemical Industries Co., Ltd.), 70 g (0.017 mol, weight average fraction) Submount (in terms of polystyrene) (measured by means of GPC): 4,600) macromonomer (1-3) added to 233 g of 1-methoxy-2-propanol, followed by 80 ° C Heat under a nitrogen/air stream. Next, 1.54 g (7.6 mmol) of dodecanethiol and 0.5 g of dimethyl 2,2'-azobisisobutyrate (V-601 (trade name), by Wako Pure Chemical Industries, were added thereto. (manufactured by Ltd.), followed by stirring for 2 hours. Next, 0.5 g of dimethyl 2,2'-azobisisobutyrate (V-601 (trade name), manufactured by Wako Pure Chemical Industries, Ltd.) was added thereto, followed by stirring for 2 hours. Next, 0.5 g of dimethyl 2,2'-azobisisobutyrate (V-601, manufactured by Wako Pure Chemical Industries, Ltd.) was added thereto, followed by raising the temperature to 90 ° C and stirring for 2 hours. Thus, a 30% by mass solution of the resin (1-10) in 1-methoxy-2-propanol was obtained.

The resin (1-10) had a weight average molecular weight of 31,000 (measured by means of GPC measurement), a number average molecular weight of 14,000, and an acid value of 82 mg KOH/g.

The resin (1-1) to the resin (1-10) are resins of the (B1-1) copolymer belonging to the (B1) specific resin of the first aspect of the invention.

The comparative resin (1-1) is a resin which does not have any of a phosphate group and a sulfonic acid group in the molecule.

In the following, the structure of the raw material monomers used in the synthesis is shown.

Subsequently, in the (B1) specific resin, a method of synthesizing a resin belonging to the (B1-2) resin will be described. The resin (1-11) as the (B1-2) resin was synthesized according to the following procedure.

[Synthesis Example 1-11: Synthetic Resin (1-11)]

112.5 g (0.15 mol) with 750 number average molecular weight polyethylene glycol monomethyl ether, 68.4 g (0.60 mol) ε-caprolactone and 0.18 g dibutyltin laurate heated under nitrogen at 160 ° C At 20 hours, a polyether-polyester monohydroxy product was obtained. Its weight average molecular weight measured by means of GPC measurement was 2,300, and its number average molecular weight was 1,100. Next, 7.0 g of polyphosphoric acid containing 84% of phosphorus pentoxide was added to 100 g of the obtained polyether-polyester monohydroxy product, and then reacted at 80 ° C for 5 hours while removing water to obtain a resin ( 1-11).

The obtained resin (1-11) had a weight average molecular weight of 2,500 (measured by means of GPC measurement) and a number average molecular weight of 1,200. The ratio of the presence of the phosphoric acid monoester to the phosphodiester (i.e., the phosphoric acid monoester: phosphodiester) was found to be 88:12 by ³¹ P NMR.

[Synthesis Example 1-12: Synthetic Resin (1-12)]

112.5 grams (0.15 moles) with 750 number average molecular weight polyethylene glycol monomethyl ether, 61.6 grams (0.54 moles) ε-caprolactone, 6.8 grams (0.068 moles) δ-valerolactone and 0.18 grams of laurel Dibutyltin acid was heated at 160 ° C for 20 hours under a nitrogen atmosphere to obtain a polyether-polyester monohydroxy product. Its weight average molecular weight measured by means of GPC measurement was 2,200, and its number average molecular weight was 1,100. Next, 7.0 g of polyphosphoric acid containing 84% of phosphorus pentoxide was added to 100 g of the obtained polyether-polyester monohydroxy product, and then reacted at 80 ° C for 5 hours while removing water to obtain a resin (1). -12).

The obtained resin (1-12) had a weight average molecular weight of 2,400 (measured by means of GPC measurement) and a number average molecular weight of 1,300. The ratio of the presence of the phosphoric acid monoester to the phosphodiester (i.e., the phosphoric acid monoester: phosphodiester) was found to be 89:11 by ³¹ P NMR.

[Example 1-1 to Examples 1-18 and Comparative Example 1-1]

Preparation of black curable composition

Preparation of (A1) inorganic pigment dispersion

The components shown in the following compositions 1-I were subjected to a high viscosity partitioning process using two rolls to obtain a dispersion. In addition, it can be kneaded by a kneader for 30 minutes before the high viscosity distribution process.

(composition 1-I)

钛Titanium black having an average primary particle diameter of 40 nm (manufactured by Mitsubishi Materials Corporation) (PIGMENT BLACK 35 (trade name))    40 copies

̇(B1) specific resin or a 30% by mass solution of a comparative example resin in propylene glycol 1-monomethyl ether 2-acetate 5 parts

(The type of resin used is shown in Table 2)

The components shown in the following composition 1-II were added to the obtained dispersion, followed by stirring at 3,000 rpm for 3 hours using a homogenizer. Then, the obtained mixed solution was finely dispersed with 0.3 mm of zirconia beads for 4 hours using a dispersing device (trade name: DISPERMAT, manufactured by VMA-GETZMANN GMBH) to obtain a titanium black dispersion (hereinafter referred to as TB dispersion 1) ).

(composition 1-II)

30% by mass of a solution of any one of the resins (1-1) to (1-12) and the comparative example resin in propylene glycol 1-monomethyl ether 2-acetate 20 parts

Propylene glycol monomethyl ether acetate 150 parts

2. Preparation of a hardening composition

The following composition components were mixed with a mixer to produce the black curable compositions [(B1-1) to (B1-18) and (B1-21)] of Examples 1-1 to 1-18 and Comparative Example 1-1] .

30% by mass of a hydrazine-soluble resin (the compound shown in Table 2) in propylene glycol 1-monomethyl ether 2-acetate [(E1) alkali-soluble resin] 10 parts

Di-isopentaerythritol hexaacrylate [(C1) polymerizable compound] 2.0 parts

Isofovalol triacrylate [(C1) polymerizable compound] 1.0 part

̇Polymerization initiator (compound shown in Table 2) [(B1) photopolymerization initiator] 0.3 parts

̇TB dispersion (dispersion obtained above) 24 parts

Propylene glycol monomethyl ether acetate 10 parts

̇3-Ethyl ethoxypropionate 8 parts

̇γ-Methyl propylene methoxypropyltrimethoxy decane 0.1 part

Example 1-19

[Preparation of black curable composition (B1-19)]

Preparation of silver tin composition

15 g of tin colloid (average particle: 20 nm, solid content: 20% by weight, manufactured by Sumitomo Osaka Cement Co., Ltd.), 60 g of silver colloid (average particle: 7 nm, solid content: 20% by weight) A solution prepared by sumitomo Osaka Cement Co., Ltd. and 0.75 g of polyvinylpyrrolidone dissolved in 100 ml of water was added to 200 ml of pure water which had been heated to 60 ° C to form a colloidal solution.

Next, the colloidal solution was stirred while maintaining at 60 ° C for 60 minutes, and then irradiated with ultrasonic waves for 5 minutes. The colloidal solution was then concentrated by centrifugation to obtain a solution A having a solid content of 25%. The solution A was dried by freeze drying to obtain a sample of silver tin powder.

The black curable composition (B1-19) of Examples 1 to 19 was prepared in the same manner as in Example 1-1 except that the silver tin powder obtained by dispersing the resin (1-1) was used instead of dispersing titanium black. To obtain a silver tin dispersion.

[Example 1-20]

[Preparation of black curable composition (B1-20)]

Preparation of titanium black-red pigment composition

(Preparation of red pigment dispersion)

The following composition was subjected to fine dispersion treatment for 4 hours using a 0.3 mm zirconia bead using a dispersing machine (trade name: DISPERMAT, manufactured by VMA-GETZMANN GMBH) to obtain a red pigment dispersion.

̇C.I. Pigment Red 254 [(F1) coloring component] (described as PR254 in Table 2) 30 parts by mass

Neodymium resin solution (benzyl methacrylate / methacrylic acid / hydroxyethyl methacrylate copolymer, molar ratio: 80 / 10/10, Mw: 10000, solvent: propylene glycol methyl ether acetate 60%, resin solid content concentration: 40%) 10 parts by mass

̇ Solvent: propylene glycol methyl ether acetate 200 parts by mass

̇Dispersant: 30% by mass solution of resin (1-1) in propylene glycol 1-methyl ether 2-acetate 30 parts by mass

(Preparation of a hardening composition)

The black curable composition (B1-20) of Example 20 was prepared in the same manner as in Example 1-1 except that 20 parts of the titanium black pigment dispersion obtained by using the resin (1-1) and 4 were used. A mixture of parts of the red pigment dispersion replaces the TB dispersion.

[Comparative Example 1-2]

Preparation of black curable composition using carbon black

A black curable composition (B1-22) was prepared in the same manner as in Example 1-1 except that the titanium black used in Example 1-1 was changed to carbon black (TOKAI BLACK 7400 (trade name), by Manufactured by Tokai Carbon Co., Ltd., average primary particle diameter: 28 nm) to prepare a carbon black (CB) dispersion.

The structures of the polymerization initiators (I-1) to (I-6) and the alkali-soluble resins (D-1) and (D-2) shown in Table 2 are shown below.

Fabrication and evaluation of light-shielding films for wafer-level lenses

A resin film for forming a lens is formed using a resin for forming a lens by the following procedure to evaluate adhesion to a lens film or the like.

<1. Forming a thermosetting resin film>

The curable compositions 1 to 4 (2 ml) containing the components shown in Table 3 were applied to a 5 cm × 5 cm glass substrate (thickness: 1 mm, BK7, manufactured by Schott Glass Technologies, Inc.). It was heated at 200 ° C for 1 minute and hardened to form a resin film (films 1 to 4) for forming a lens, whereby the residue on the lens can be evaluated.

<2. Forming a photocurable resin film>

The sclerosing compositions 5 and 6 (2 ml) shown in Table 3 were applied on a 5 cm x 5 cm glass substrate, and hardened by irradiation with a metal halide lamp at 3000 mJ/cm 2 . A resin film (films 5 and 6) for forming a lens is formed, so that the residue on the lens can be evaluated.

<3. Evaluation of Resin Film for Forming Lens>

The number of coating rotations of the spin coating was adjusted so that the film thickness was 2.0 μm after the coating/heat treatment, and the black curable compositions (B1-1) to (B1-22) were uniformly coated thereon. A glass wafer [support] for forming a resin film (film 5) for the lens was formed, and heat treatment was performed on the hot plate at a surface temperature of 120 ° C for 120 seconds. Thus, a coating film [black curable composition layer] having a film thickness of 2.0 μm was obtained. Further, with respect to the black curable composition (B1-17) obtained in Example 1-17, the resin film (film 5) for forming a lens and each of the film 1 to the film 4 and the film 6 were subjected to The evaluations were the same and the results are shown in Table 4 below as Examples 1-17-1 through Examples 1-17-6.

Further, in the following table, for example, "film 1" is indicated as "1".

[Exposure step]

Subsequently, by using a high pressure mercury lamp, via a reticle having a pattern of 10 mm holes, the exposure is changed at an interval of 50 mJ/cm 2 starting at 100 mJ/cm 2 The obtained coating was exposed.

[Development Step]

After the above exposure, the coating was subjected to paddle development using a 0.3% aqueous solution of tetramethylammonium hydroxide at 23 ° C for 60 seconds, followed by rinsing with a spin shower, and then with pure The water was washed to obtain a light-shielding film having a pattern shape.

The formed light-shielding film was evaluated according to the following criteria, and the results are shown in Table 4 below.

Evaluating developability on a resin film for forming a lens

The developed portion having a 10 mm hole pattern was observed by means of SEM, and the number of residues was measured. The smaller the number of residues, the better the developability.

Evaluation of adhesion sensitivity by exposure

The minimum exposure amount which does not cause the formed light-shielding film to peel off from the substrate is evaluated as the adhesion sensitivity. The smaller the value of the sensitivity, the higher the sensitivity to the cured film adhered to the substrate.

Evaluating the adhesion to the resin film used to form the lens

Evaluation was based on a grid test based on ISO 2409 (1992).

A resin for forming a lens (film 1 to film 5) was formed on a 10 × 10 cm glass substrate in the same manner as described above. Next, the black curable composition (B1-1) To (B1-22) applied to the resin film for forming a lens shown in Table 4 to a film thickness of 2 μm, and irradiated with a high-pressure mercury lamp at 1000 mJ/cm 2 to be used in the resin for forming a lens A light-shielding film is formed on the film. Next, 10 x 10 squares were made at a distance of 1.0 mm and adhered to a cellophane tape and pulled up to check for peeling. Check the unpeeled squares. The higher the number of remaining squares, the better the adhesion is evaluated.

Evaluation of shading characteristics

The light-shielding property is expressed as the maximum transmittance of a light-shielding film having a thickness of 2 μm to light having a wavelength of 400 nm to 800 nm. The higher the value, the better the light-shielding property is evaluated, and therefore, the transmittance of less than 1% is actually judged to be a good level.

As can be seen from Table 4, the black hardening for wafer level lenses of the present invention The light-shielding film formed of the composition has excellent developability, good pattern formation characteristics, and excellent adhesion sensitivity and adhesion on the resin film for forming a lens, and thus has excellent adhesion to the lens. In addition, all of the light-shielding films formed have excellent light-shielding properties.

Example of the second aspect

Preparation of black curable composition

Preparation of (B2) dispersible resin

[Synthesis Example 2-1: Synthetic Resin (2-1)]

The resin (2-1) which is the (B2) specific resin which is the second aspect of the present invention is synthesized by using the phosphate group-containing monomer (2-1) and the macromonomer (2-1) according to the following scheme.

Next, 15 g (0.072 mol) of monomer (2-1) (PHOSMER M (trade name), manufactured by Unichemical Co., Ltd.), 85 g (0.057 mol, weight average molecular weight (in terms of polystyrene) (measured by means of GPC): 3,100) The macromonomer (2-1) was added to 233 g of 1-methoxy-2-propanol, followed by heating at 80 ° C under a nitrogen/air stream. Next, 1.54 g (7.6 mmol) of dodecanethiol and 0.5 g of dimethyl 2,2'-azobisisobutyrate (V-601 (trade name), by Wako Pure Chemical Industries, were added thereto. (manufactured by Ltd.), followed by stirring for 2 hours. Next, 0.5 g of dimethyl 2,2'-azobisisobutyrate (V-601 (trade name), manufactured by Wako Pure Chemical Industries, Ltd.) was added thereto, followed by stirring for 2 hours. Next, 0.5 g of dimethyl 2,2'-azobisisobutyrate (V-601, by Wako Pure Chemical) was added thereto. (manufactured by Industries, Ltd.), and then the temperature was raised to 90 ° C, and stirred for 2 hours, thereby obtaining a 30 mass% solution of the resin (2-1) in 1-methoxy-2-propanol.

The resin (2-1) had a weight average molecular weight of 25,000 (measured by means of GPC measurement), a number average molecular weight of 11,000, and an acid value of 40 mg KOH/kg (first-order dissociation).

[Synthesis Examples 2-2 to 2-9: Synthetic Resin (2-2) to Resin (2-9)]

Resin (2-2) to resin (2-9) were obtained in the same manner as in Synthesis Example 2-1 except that the monomers and macromonomers shown in Table 5 were used. The weight average molecular weight, number average molecular weight, and acid value (first-order dissociation value when phosphoric acid is contained) of the obtained resin are shown in Table 5.

The weight average molecular weight of the macromonomer (2-1) was 3,100 as described above, and the weight average molecular weight of the macromonomer (2-3) was 4,600 as described below.

[Synthesis Example 2-10: Synthetic Resin (2-10)]

The resin (2-10) which is the specific resin of the (B1) of the second aspect of the present invention is synthesized by using the phosphate group-containing monomer (2-5) and the macromonomer (2-3) according to the following scheme.

Next, 15 grams (0.072 moles) of monomer (2-5), 85 grams (0.021 moles, weight average molecular weight (in terms of polystyrene) (measured by means of GPC): 4,600) The macromonomer (2-3) was added to 233 grams of N-methyl-2-pyrrolidone, followed by heating at 80 ° C under a stream of nitrogen/air. Next, 1.54 g (7.6 mmol) of dodecanethiol and 0.5 g of dimethyl 2,2'-azobisisobutyrate (V-601 (trade name), by Wako Pure Chemical Industries, were added thereto. (manufactured by Ltd.), followed by stirring for 2 hours. Next, 0.5 g of dimethyl 2,2'-azobisisobutyrate (V-601 (trade name), manufactured by Wako Pure Chemical Industries, Ltd.) was added thereto, followed by stirring for 2 hours. Next, 0.5 g of dimethyl 2,2'-azobisisobutyrate (V-601, manufactured by Wako Pure Chemical Industries, Ltd.) was added thereto, and then the temperature was raised to 90 ° C, and stirred for 2 hours. And the polymerization solution was reprecipitated with 2 liters of water, followed by drying. The obtained resin was dissolved in 1-methoxy-2-propanol to obtain a 30% by mass solution of the resin (2-10) in 1-methoxy-2-propanol.

The resin (2-10) had a weight average molecular weight of 31,000 (measured by means of GPC measurement), a number average molecular weight of 14,000, and an acid value of 41 mg KOH/g.

The weight average molecular weight, number average molecular weight, and acid value (first-order dissociation value when phosphoric acid is contained) of the obtained resin are shown in Table 5.

The resin (2-1) to the resin (2-10) are resins of the (B2-1) copolymer belonging to the (B2) specific resin of the second aspect of the present invention.

[Synthesis Example 2-11: Synthetic Resin (2-11)]

112.5 g (0.15 mol) with 750 number average molecular weight polyethylene glycol monomethyl ether, 68.4 g (0.60 mol) ε-caprolactone and 0.18 g dibutyltin laurate heated under nitrogen at 160 ° C At 20 hours, a polyether-polyester monohydroxy product was obtained. Its weight average molecular weight measured by means of GPC measurement was 2,300, and its number average molecular weight was 1,100. Next, 7.0 g of polyphosphoric acid containing 84% of phosphorus pentoxide was added to 100 g of the obtained polyether-polyester monohydroxy product, and then reacted at 80 ° C for 5 hours while removing water to obtain a resin (2). -11).

The obtained resin (2-11) had a weight average molecular weight of 2,500 (measured by means of GPC measurement) and a number average molecular weight of 1,200. The content ratio of phosphate monoester to phosphodiester (phosphoric acid monoester: phosphodiester) was determined by ³¹ P NMR to be 88:12. The acid value is 50 mg KOH/g (a primary dissociation value when phosphoric acid is included). The acid value of the obtained resin (which is a primary dissociation value when phosphoric acid is contained) is shown in Table 5.

[Synthesis Example 2-12: Synthetic Resin (2-12)]

112.5 grams (0.15 moles) with 750 number average molecular weight polyethylene glycol monomethyl ether, 61.6 grams (0.54 moles) ε-caprolactone, 6.8 grams (0.068 moles) δ-valerolactone and 0.18 grams of laurel Dibutyltin acid was heated at 160 ° C for 20 hours under a nitrogen atmosphere to obtain a polyether-polyester monohydroxy product. Its weight average molecular weight measured by means of GPC measurement was 2,200, and its number average molecular weight was 1,100. Next, 7.0 g of polyphosphoric acid containing 84% of phosphorus pentoxide was added to 100 g of the obtained polyether-polyester monohydroxy product, and then reacted at 80 ° C for 5 hours while removing water to obtain a resin ( 2-12).

The obtained resin (2-12) had a weight average molecular weight of 2,400 (measured by means of GPC measurement) and a number average molecular weight of 1,300. The ratio of the presence of the phosphoric acid monoester to the phosphodiester (i.e., the phosphoric acid monoester: phosphodiester) was found to be 89:11 by ³¹ P NMR. The acid value was 48 mg KOH/g (a primary dissociation value when phosphoric acid was included). The acid value of the obtained resin (which is a primary dissociation value when phosphoric acid is contained) is shown in Table 5.

[Synthesis Examples 2-13, 2-14, 2-16, 2-17, 2-22, and 2-23: Synthetic Resins (2-13), (2-14), (2-16), (2- 17), (2-22) and (2-23)]

Resin (2-13), (2-14), (2-16), (2-17), (2-22), and (2-23) were synthesized in the same manner as in Synthesis Example 2-1. The exception is that the amount of monomer (2-1) and macromonomer (2-1) used is changed to the amount shown in Table 5.

[Synthesis Example 2-15: Synthetic Resin (2-15)]

First, 5 g (0.024 mol) of monomer (2-1) (PHOSMER M (trade name), manufactured by Unichemical Co., Ltd.), 10 g (0.048 mol) of monomer (2-5) ( Product of Tokyo Chemical Industry Co., Ltd.) and 85 g (0.021 mol, weight average molecular weight (in terms of polystyrene) measured by GPC: 4,600) macromonomer (2-3) was added to It was heated in 233 g of N-methyl-2-pyrrolidone followed by a stream of nitrogen/air at 80 °C. Next, 1.54 g (7.6 mmol) of dodecanethiol and 0.5 g of dimethyl 2,2'-azobisisobutyrate (V-601 (trade name), by Wako Pure Chemical Industries, were added thereto. (manufactured by Ltd.), followed by stirring for 2 hours. Next, 0.5 g of dimethyl 2,2'-azobisisobutyrate (V-601 (trade name), manufactured by Wako Pure Chemical Industries, Ltd.) was added thereto, followed by stirring for 2 hours. Then, 0.5 g of dimethyl 2,2'-azobisisobutyrate (V-601, manufactured by Wako Pure Chemical Industries, Ltd.) was added thereto, and then the temperature was raised to 90 ° C, and stirred for 2 hours. The polymerization solution was reprecipitated with 2 liters of water and then dried. The obtained resin was dissolved in 1-methoxy-2-propanol to obtain a 30% by mass solution of the resin (2-15) in 1-methoxy-2-propanol. The weight average molecular weight measured by GPC measurement was 29,000, the number average molecular weight was 12,000, and the acid value was 39 mgKOH/g.

[Synthesis Example 2-18 to 2-21: Synthetic Resin (2-18) to Resin (2-21)]

Resin (2-18) to resin (2-21) were synthesized in the same manner as in Synthesis Example 2-1 except that macromonomers (2-4) to macromonomers as described below were respectively used. The bulk (2-7) was substituted for the macromonomer (2-1) used in Synthesis Example 2-1.

The structure of the raw material monomer used in the synthesis (B2) of the specific resin and the comparative resin is shown below.

[Example 2-1 to Example 2-37 and Comparative Example 2-1 to Comparative Example 2-3]

Preparation of black curable composition

[Preparation of inorganic pigment dispersion A]

The components shown in the following composition 2-I were subjected to a high viscosity partitioning process using two rolls to obtain a dispersion. In addition, it can be kneaded by a kneader for 30 minutes before the high viscosity distribution process.

(composition 2-I)

̇Titanium Black A or Titanium Black B 40 parts

30% by mass of a specific resin or comparative resin in propylene glycol 1-monomethyl ether 2-acetate

(The categories of specific resins or comparative resins are as shown in Table 6).

Titanium black A is TITANIUM BLACK 12S (trade name) manufactured by Mitsubishi Materials Corporation (average initial particle diameter: 60 nm), and titanium black B is TITANIUM BLACK 13 MT (trade name) manufactured by Mitsubishi Materials Co., Ltd. ) (average initial particle diameter: 90 nm). The comparative resin DISPERBYK-180 (trade name) of Comparative Example 2-1 was a dispersant manufactured by BYK Additives & Instruments and was a resin not containing a phosphate group and a sulfonic acid group.

The components shown in the following composition 2-II were added to the obtained dispersion, followed by stirring at 3,000 rpm for 3 hours using a homogenizer. The obtained mixed solution was subjected to fine dispersion treatment using a dispersing machine (trade name: DISPERMAT (trade name), manufactured by VMA-GETZMANN GMBH) using 0.3 mm zirconia beads for 4 hours to obtain a titanium black dispersion (hereinafter referred to as TB dispersion A).

(Composition 2-II)

30% by mass solution of oxime resin (2-1) to (2-23) in propylene glycol 1-monomethyl ether 2-acetate 30 parts

Propylene glycol monomethyl ether acetate 150 parts

[Preparation of inorganic pigment dispersion 2-B to 2-F]

The inorganic pigment dispersion 2-B to 2-F was prepared in the same manner as in the preparation of the inorganic pigment dispersion A, except for the titanium black A or titanium black used in the preparation of the composition 2-I of the inorganic pigment dispersion A. The amount of B and the specific resin or comparative resin was changed so that the mass ratio of the specific resin to titanium black A or titanium black B was the value shown in Table 6.

Preparation of black curable composition

The components in the following compositions were mixed with a stirrer to obtain black curable compositions (B2-1) to (B2-19), (B2-22) to (B2-36), (B2-39) and B2-40) (see Table 6).

a 30% by mass solution of a hydrazine-soluble resin (the compound shown in Table 6) in propylene glycol 1-monomethyl ether 2-acetate 10 parts

Diisopentaerythritol hexaacrylate [(C2) polymerizable compound] 2.0 parts

̇isoamyl alcohol triacrylate [(C2) polymerizable compound] 1.0 part

̇Polymerization initiator (compound described in Table 6) [(B2) photopolymerization initiator] 0.3 parts

̇Inorganic pigment dispersion (such as the inorganic pigment dispersion described above) 24 parts

Propylene glycol monomethyl ether acetate 10 parts

̇3-Ethyl ethoxypropionate 8 parts

̇γ-Methyl propylene methoxypropyltrimethoxy decane 0.1 part

[Preparation of black curable composition]

A black curable composition (B2-37) was prepared in the same manner as in the preparation of the black curable composition (B2-1), with the exception of (C2) which would be used for the preparation of the black curable composition (B2-1). The amount of the polymerizable compound diisopentaerythritol hexaacrylate and pentaerythritol triacrylate was changed to 0.5 part, respectively, and the amount of the alkali-soluble resin was changed to 16.7 parts, thereby including the black curable composition. The content of the (C2) polymerizable compound was changed to 9% by mass.

Further, a black curable composition (B2-38) was prepared in the same manner as in the preparation of the black curable composition (B2-1), with the exception that it was used for the preparation of the black curable composition (B2-1) ( C2) The amount of the polymerizable compound diisopentaerythritol hexaacrylate and isopentaerythritol triacrylate is changed to 3 parts, respectively, and the alkali-soluble resin is not added, so that the black curable composition is included (C2) The content of the polymerizable compound was changed to 51% by mass.

[Preparation of black curable composition (B2-20)]

<Preparation of silver tin composition>

15 g of tin colloid (average particle: 20 nm, solid content: 20% by weight, by Sumitomo Osaka Cement Co., Ltd.), 60 g of silver colloid (average particle: 7 nm, solid content: 20% by weight, manufactured by Sumitomo Osaka Cement Co., Ltd.) and 0.75 g of polyvinylpyrrolidone A solution in 100 ml of water was added to 200 ml of pure water which had been heated to 60 ° C to obtain a colloidal solution.

Next, the colloidal solution was stirred while maintaining at 60 ° C for 60 minutes, and then irradiated with ultrasonic waves for 5 minutes. Next, the colloidal solution was concentrated by centrifugation to obtain a solution A having a solid content of 25%. The solution A was dried by freeze drying to obtain a sample of silver tin powder.

A black curable composition (B2-20) was prepared in the same manner as in the preparation of the black curable composition (B2-1), except that the silver tin powder obtained by dispersing the resin (2-1) was used instead of dispersing titanium. Black, a silver tin dispersion was obtained.

[Preparation of black curable composition (B2-21)]

The black curable composition (B2-21) was obtained in the same manner as in the preparation of the black curable composition (B2-11) except that the amount of the resin (2-11) in the composition (2-II) was changed. It was 50 parts, and the addition amount of the alkali-soluble resin was changed to 3 parts.

As the resin (D-1) and resin (D-2) of the alkali-soluble resin shown in Table 6 below, and the initiator (I-1) to the initiator (I-6), in the example of the first aspect The same is used.

Production of light-shielding film and solid-state imaging element

<Manufacturing substrate A and substrate B>

(Manufacture of substrate A)

Substrate A was fabricated in the following manner to verify the development residue in the solid-state photographic element (in the form of no solder resist layer on the back side) of an embodiment as described above.

That is, a circular metal electrode made of copper (Cu) having a thickness of 5 μm and a diameter of 10 μm was obtained on the tantalum substrate by micromachining (photolithography) technique, sputtering method, and electroplating technique.

Therefore, as shown in the schematic cross-sectional view of FIG. 11, the substrate A having the plurality of circular metal electrodes 310 is obtained on the ruthenium substrate 300.

(Manufacture of substrate B)

The substrate B was fabricated in the following manner to verify the development residue in the solid-state photographic element (in the form of a solder resist layer on the back side) of one of the embodiments described above.

A solder resist layer having a circular pattern of 10 μm was formed on the side of the substrate A on which the circular metal electrode was formed by photolithography using the following solder resist.

As the pattern of the solder resist layer, a pattern having an opening exposing a part of the metal electrode as shown in Fig. 13 was employed.

Therefore, as shown in the schematic cross-sectional view of FIG. 13, the substrate B having the configuration of the circular metal electrode 310 and the solder resist layer 330 is obtained on the ruthenium substrate 300.

The components of the solder resist are as follows.

The following resin solution 155 parts by mass

2-(ethyloxyiminomethyl) thioxan-9-one (photopolymerization initiator) 2 parts by mass

2-methyl-1-[4-(methylthienyl)]-2-(N-morpholinyl)propan-1-one (photopolymerization initiator) 6 parts by mass

2,4-diethyl 9-thioxanthene (sensitizer) 1 part by mass

C.I. Pigment Blue 15:6 (colorant) 0.9 parts by mass

C.I. Pigment Yellow 199 (colorant) 2.3 parts by mass

Diisopentaerythritol hexaacrylate (monomer) 20 parts by mass

Trimethylolpropane triacrylate (monomer) 10 parts by mass

Barium sulfate (filler) 130 parts by mass

Phenol varnish type novolac epoxy resin (EPPN-201, manufactured by Nippon Kayaku Co., Ltd.) (thermosetting component) 15 parts by mass

Bixylenolepoxy resin (YX-4000 (trade name), manufactured by Epoxy Resins Co., Ltd.) 30 parts by mass

Melamine 3 parts by mass

Dipropylene glycol methyl ether acetate 5 parts by mass

#150 (trade name) (aromatic organic solvent, manufactured by Idemitsu Petrochemical Co., Ltd.) 5 parts by mass

(Preparation of resin solution)

First, 660 g of cresol novolac epoxy resin (EOCN-104S (trade name), manufactured by Nippon Kayaku Co., Ltd.), 421.3 g of carbitol acetate, and 180.6 g of solvent petroleum spirit were fed, followed by Heat/stirred at 90 ° C to dissolve. Next, the mixture was cooled to 60 ° C, and 216 g of acrylic acid, 4.0 g of triphenylphosphine, and 1.3 g of p-methoxyphenol were added thereto, followed by reaction at 100 ° C for 12 hours. At this time, the acid value is 0.3 mg KOH / g. Then, 241.7 g of tetrahydrophthalic anhydride was added thereto, followed by heating to 90 ° C and reacting for 6 hours. Thus, a solid content concentration of 65% by mass, a solid content of 77 mg KOH/g, and a double bond equivalent (resin weight per gram of unsaturated groups (g)) of 400 g/equivalent and weight were obtained. A resin solution having an average molecular weight of 8,000.

<Manufacture of a light-shielding film>

The above-described black curable composition prepared in the examples and comparative examples shown in Table 7 was spin-coated onto the surface of the substrate A to the substrate B on which the metal electrode was formed, and then on the hot plate at 120 ° C. The mixture was heated for 2 minutes to obtain a black curable composition coating.

The resulting coating is then passed through an i-ray stepper exposure apparatus, via a reticle for forming a 10 micron circular pattern, in the range of 100 mJ/cm to 1000 mJ/cm, 50 Exposure is performed by varying the amount of exposure in millijoules per square centimeter.

Subsequently, the exposed coating was subjected to mixed development using a 0.3% aqueous solution of tetramethylammonium hydroxide at 23 ° C for 60 seconds, followed by rinsing with a rotary water jet, and then washing with pure water to obtain a shading having a pattern shape. Sex film.

Herein, a light-shielding film having an opening pattern is formed which exposes a part of the metal electrode 310 as shown in FIG. 12 (the light-shielding film 320 in FIG. 12).

Herein, a light-shielding film having an opening pattern is formed, the opening exposing a portion of the metal electrode 310 as shown in FIG. 14 (specifically, when viewed in a direction perpendicular to the substrate, the pattern overlaps with the solder resist layer; The light-shielding film 340 in 14).

Evaluation

The light-shielding films produced in the examples and comparative examples were evaluated in the following manner. The results of the evaluation are shown in Table 7.

(evaluating adhesion)

For the light-shielding films formed in the respective examples and comparative examples, the minimum exposure amount at which no peeling occurred on the side of the ruthenium substrate was evaluated as the adhesion sensitivity. The smaller the value of adhesion sensitivity, the smaller The higher the substrate adhesion.

The smaller the value of the adhesion sensitivity, the higher the adhesion of the substrate.

Further, for the minimum exposure amount in which no peeling occurred, the exposure amount during development was gradually increased, and irradiation was performed in an exposure amount corresponding to each step, and in this case, vertical 100 μm × horizontal 100 μm was observed by means of SEM. In the region, the condition in which all the patterns are formed without defects is expressed as "no peeling", and the exposure amount under the irradiation is expressed as "the minimum exposure amount in which no peeling occurs".

(evaluation step)

In the examples and comparative examples, when the development was performed for the minimum exposure amount (so that the light-shielding film on the side of the substrate was not peeled off), the substrate A to the light-shielding film produced on the substrate B was observed by means of SEM. 20 cross sections, and the width of the step zone is measured by the average. The narrower the width of the step zone, the better the shading capability of the central portion and the peripheral portion.

Further, the area where the film thickness becomes 90% or less of the central portion of the light-shielding film is measured by the step area.

(assessing the residue)

In the examples and comparative examples, the range of 500 μm × 500 μm on the exposed metal was observed by means of SEM, which was when development was performed for the minimum exposure amount (so that the light-shielding film on the side of the substrate was not peeled off). An area other than the area where the light-shielding film has been formed is formed, and the number of residues is counted. The smaller the number of residues, the better the developability is indicated.

(Evaluating shading characteristics)

In the examples and comparative examples, a light-shielding film which has been prepared on the substrate A to the substrate B before development, and a wavelength of 700 nm to 1200 nm were measured with a spectrophotometer (UV23600 (trade name), manufactured by Shimadzu Corporation). The maximum transmittance in the zone. The smaller the value, the better the result. A condition in which the maximum transmittance is less than 1% indicates that the light shielding property is good.

As can be seen from the above Table 7, by using the black curable composition of the present invention, the ability to block infrared light is excellent, and the residue in the unexposed portion (the residue outside the region where the light-shielding film is formed) can be reduced, facing The adhesion of the substrate is excellent and the step is reduced.

Further, in comparison with Examples 2-8 and 2-9, which were prepared using the same monomers and macromonomers and using a specific resin having an acid value in the range of 20 mgKOH/g to 70 mgKOH/g, in Example 2 -1 to 2-7 using an acid value of 20 mg KOH / g to A specific resin of 70 mg KOH/g can help improve adhesion to the ruthenium substrate and reduce residue, especially steps.

Further, in Examples 2 to 11 and Examples 2 to 10, in which the same components were used, except that the specific resin having the structure of the formula (I) was not used, Examples 2 to 11 and Examples 2 to 12 (wherein The inhibition of steps and residues in the specific resin of the formula (I) is further improved.

Example 2-38: Manufacturing and Evaluating Solid State Photographic Components

<Manufacture of solid-state photographic elements>

Preparation of color hardening composition

Red (R) hardenable composition 2-C-1, green (G) hardenable composition 2-C-2, and blue (B) hardenable composition were prepared in the same manner as in Example 2-1. 2-C-3, except that titanium black 12S (manufactured by Mitsubishi Materials Co., Ltd.) used as a black pigment used in the black curable composition (B2-1) used in Example 2-1 was changed to The following color pigments.

Color pigment used to form color pixels for each of RGB

Eosin (R) pigment: C.I. Pigment Red 254

̇Green (G) pigment: C.I. Pigment Green 36 and C.I. Pigment Yellow 139 70/30 [mass ratio] mixture

Indigo (B) pigment: C.I. Pigment blue 15:6 and C.I. Pigment Violet 23 70/30 [mass ratio] mixture

Manufacturing full color color filters for solid state imaging elements

A 1.0 μm × 1.0 μm green (G) pattern was formed on the side of the substrate B fabricated in Example 2-1 without forming a light-shielding film in the same manner as in the method described in Example 2-4, with the exception of use. Green (G) color curable composition 2-C-2, a mask of 1.0 micron x 1.0 micron Bayer pattern was used. In addition, in the same manner (except for the mask using a 1.0 micron × 1.0 micron island pattern), a red (R) color pattern and a blue (B) color pattern are sequentially formed, thereby making a whole for solid-state imaging elements. Color filter.

Evaluation

The obtained full-color color filter for solid-state photographic elements was incorporated into a solid-state photographic element, and the solid-state photographic element was found to have high resolution and excellent color separation. In addition, as described above, the light-shielding film produced in the examples has excellent infrared light-shielding effect and can be beneficial for reducing residues, so that it is also advantageous to reduce noise and residual caused by infrared light. The noise caused by the object.

Example of the third aspect

[Synthesis Example 3-1: Synthetic Resin (3-1) (P-Q type)]

Adding 56 grams (0.56 moles) of methyl methacrylate and 6.39 grams (0.029 moles) of chain transfer agent (a) to 233 grams of propylene glycol monomethyl ether acetate (hereinafter referred to as PGMEA), followed by nitrogen/air The mixture was heated at 80 ° C for 1 hour. Next, 1.48 g (0.0090 mol) of azobisisobutyronitrile was added thereto, followed by heating and stirring for 3 hours and then heating at 120 ° C for 2 hours. At this time, the weight average molecular weight (Mw) of the resin (corresponding to the solvent compatibility portion) was 2,500. Next, 44 g (0.28 mol) of 2-dimethylaminoethyl methacrylate was added, and 1.48 g (0.0090 mol) of azobisisobutyronitrile was further added thereto, followed by stirring for 3 hours and then at 120 °C. The mixture was heated for 2 hours to obtain a 30 mass% solution of the resin (3-1) in PGMEA. The weight average molecular weight (Mw) was 4,600, and Mw/Mn was 1.3. Further, the weight average molecular weight (Mw) of the pigment adsorbing moiety is 2,100, which is equal to [4,600 (weight average molecular weight of the resin (3-1)) - 2,500 (weight average molecular weight of the solvent compatible portion)]. The amine value (titration) was 159 mg KOH/g. The synthetic process is shown below.

[Synthesis Examples 3-2 to 3-44: Synthetic Resins (3-2) to (3-44)]

Subsequently, a 30% by mass solution of the resin (3-2) to (3-44) in PGMEA was prepared in the same manner as in Synthesis Example 3-1 except for the monomer used in Synthesis Example 3-1 and The chain transfer agent was changed to the monomer used in the solvent compatible portion, the monomer used in the pigment adsorbing portion, and the chain transfer agent, respectively, in the categories and amounts as shown in Table 8 or Table 9.

In Tables 8 and 9, "P(Mw)" represents the weight average molecular weight of the solvent-compatible portion, and "Q(Mw)" represents the weight average molecular weight of the pigment-adsorbing portion. Further, "resin (Mw)" means the weight average molecular weight of each of the obtained resins, and "amine value" means the amine value of each resin.

The monomers a to i and the chain transfer agent (b) used in the synthesis examples 3-1 to 3-44 were as follows. The chain transfer agent (a) is the chain transfer agent (a) used in Synthesis Example 3-1.

[Synthesis Example 3-45: Synthetic Resin (3-45) (P-Q-P Type)]

41.5 grams (0.415 moles) of methyl methacrylate and 2.40 grams (0.011 moles) of chain transfer agent (a) were added to 233 grams of PGMEA, followed by heating at 80 ° C for 1 hour under a stream of nitrogen/air. Next, 1.48 g (0.0090 mol) of azobisisobutyronitrile was added thereto, followed by heating and stirring for 3 hours and then heating at 120 ° C for 2 hours. At this time, the weight average molecular weight (Mw) of the resin (corresponding to the solvent compatibility portion) was 4,700. Next, 17 g (0.11 mol) of 2-dimethylaminoethyl methacrylate was added, and 1.48 g (0.0090 mol) of azobisisobutyronitrile was further added thereto, followed by stirring for 3 hours. At this time, the weight average molecular weight of the resin was 7,000, and thus the weight average molecular weight of the pigment adsorbing moiety was 2,300, which was equal to [7,000-4,700]. 41.5 grams (0.415 moles) of methyl methacrylate was added thereto, and Further, 1.48 g (0.0090 mol) of azobisisobutyronitrile was added thereto, followed by stirring for 3 hours, and then heating at 120 ° C for 2 hours, thereby obtaining a 30 mass% solution of the resin (3-45) in PGMEA. The weight average molecular weight (Mw) was 12,000 and the degree of dispersion was 1.3. Further, the solvent-compatible portion has a weight average molecular weight of [12,000-7,000] = 5,000. The amine value (titration) was 61 mg KOH/g. The synthetic process is shown below.

[Synthesis Example 3-46: Synthetic Resin (3-46) (P-Q-P Type)]

41.5 grams (0.415 moles) of methyl methacrylate and 2.40 grams (0.011 moles) of chain transfer agent (a) were added to 233 grams of PGMEA, followed by heating at 80 ° C for 1 hour under a stream of nitrogen/air. Next, 1.48 g (0.0090 mol) of azobisisobutyronitrile was added thereto, followed by heating and stirring for 3 hours. At this time, the weight average molecular weight of the resin (corresponding to the solvent compatibility portion) was 4,900. Next, 17 g (0.079 mol) of monomer d was added and 1.48 g (0.0090 mol) of azobisisobutyronitrile was further added thereto, followed by stirring for 3 hours. At this time, the weight average molecular weight of the resin was 7,800, and thus, the weight average molecular weight of the pigment adsorbing moiety was 2,900, which was equal to [7,800-4,900]. Further, 41.5 g (0.415 mol) of methyl methacrylate was added thereto, and 1.48 g (0.0090 mol) of azobisisobutyronitrile was further added thereto, followed by stirring for 3 hours, thereby obtaining a resin (3-46). 30% by mass solution in PGMEA. The weight average molecular weight (Mw) was 13,000 and the degree of dispersion was 1.3. Further, the solvent-compatible portion has a weight average molecular weight of [13,000-7,800] = 5,200. The amine value (titration) was 47 mg KOH/g. The synthetic process is shown below.

[Comparative Synthesis Example 3-1: Synthetic Resin (3-47)]

First, 25 grams (0.16 moles) of 2-dimethylaminoethyl methacrylate, 75 grams (0.75 moles) of methyl methacrylate, and 2.0 grams (0.0099 moles) of dodecyl mercaptan were added to In 233 grams of PGMEA, it was then heated to 75 ° C under a nitrogen/air stream. Next, 1.48 g (0.0090 mol) of azobisisobutyronitrile was added thereto, followed by heating for 2 hours. Further, 1.48 g (0.0090 mol) of azobisisobutyronitrile was added thereto, followed by heating for 2 hours, followed by raising the temperature to 90 ° C and heating for 1 hour. The obtained solution was cooled to obtain a 30 mass% solution of the resin (3-47) in PGMEA. The resin (3-47) had an amine value of 85 mg KOH/g, a weight average molecular weight of 19,000, and a weight average molecular weight/number average molecular weight of 2.7. The synthetic process is shown below.

[Comparative Synthesis Example 3-2: Synthetic Resin (3-48)]

First, 15 grams (0.17 moles) of methacrylic acid, 85 grams (0.85 moles) of methyl methacrylate, and 2.0 grams (0.0099 moles) of dodecyl mercaptan were added to 233 grams of PGMEA, followed by nitrogen. / Heat to 75 ° C under air flow. Next, 1.48 g (0.0090 mol) of azobisisobutyronitrile was added thereto, followed by heating for 2 hours. Further, 1.48 g (0.0090 mol) of azobisisobutyronitrile was added thereto, followed by heating for 2 hours, followed by raising the temperature to 90 ° C and heating for 1 hour. Cooling the obtained solution to obtain 30 quality of resin (3-48) in PGMEA Amount of % solution. The resin (3-48) had an acid value of 100 mg KOH/g, a weight average molecular weight of 21,000, and a weight average molecular weight/number average molecular weight of 2.7. The synthetic process is shown below.

Black sclerosing composition using titanium black prepared in Example 3-1 to Example 3-52

(Preparation of dispersion)

The components shown in the following (composition 3-I) were subjected to a high viscosity partitioning process using two rolls to obtain a dispersion. In addition, it can be kneaded by a kneader for 30 minutes before the high viscosity distribution process.

(composition 3-I)

Titanium black having a mean initial particle diameter of 75 nm (13MT (trade name), manufactured by Mitsubishi Materials Co., Ltd.) (Pigment Black 35) 40 parts

Each of the enamel resins (3-1) to (3-48) is a 30% by mass solution in PGMEA 5 parts

The components shown in the following (composition 3-II) were added to the obtained dispersion, followed by stirring at 3,000 rpm for 3 hours using a homogenizer. The obtained mixed solution was finely dispersed with 0.3 mm of zirconia beads for 4 hours using a dispersing device (trade name: DISPERMAT, manufactured by VMA-GETZMANN GMBH) to obtain a titanium black dispersion.

(Composition 3-II)

30% by mass solution of each of enamel resins (3-1) to (3-48) in PGMEA 20 parts

̇ Solvent: 150 parts of PGMEA

(Preparation of black curable composition using titanium black)

Various black curable compositions using titanium black of Examples 3-1 to 3-5 were prepared by mixing the composition of the following (composition 3-III) with a stirrer.

(Composition 3-III)

Alkaloid-soluble resin: all of the resin 3-D-1 or resin 3-D-2 (structure shown below) in Table 10 and Table 30 in a 30 mass% solution in PGMEA 10 parts

̇Polymerizable compound: diisoamyltetraol hexaacrylate 2.0 parts

̇Polymerizable compound: isovalerol triacrylate 1.0 part

Cerium polymerization initiator: the compounds described in Table 10 and Table 11 (structure shown below) 0.3 parts

̇Dispersion: each dispersion shown in Table 10 and Table 24

̇ Solvent: PGMEA 10 parts

̇ Solvent: 3-ethoxypropionate ethyl ester (called EEP) 8 parts

̇γ-Methyl propylene methoxypropyltrimethoxy decane 0.1 part

̇MEGAFAC F171 0.05 parts

Preparation Example 3-53 Black Curable Composition Using Silver Tin Composition

15 g of tin colloid (average particle system: 20 nm, solid content: 20% by mass, manufactured by Sumitomo Osaka Cement Co., Ltd.), 60 g of silver colloid (average particle: 7 nm, solid content: 20 mass) %, a solution of 0.75 g of polyvinylpyrrolidone dissolved in 100 ml of water was added to 200 ml of pure water which had been heated to 60 ° C to obtain a colloidal solution.

Next, the colloidal solution was stirred while maintaining at 60 ° C for 60 minutes, and then irradiated with ultrasonic waves for 5 minutes. The colloidal solution was then concentrated by centrifugation to obtain a solution A having a solid content of 25%. The solution A was dried by freeze drying to obtain a powder sample.

Preparation of silver tin dispersion in the same manner as in the preparation of titanium black dispersion, The above powder sample was used instead of titanium black, and the resin (3-3) was used as the resin. Next, a black curable composition containing a silver tin composition was prepared in the same manner as in Example 3-1 except that a silver tin dispersion was used instead of the black hardenability for preparing titanium black containing in Example 3-1. A titanium black dispersion of the composition.

Preparation of the black curable composition of Examples 3-54

The black hardenable composition of Example 3-54 was obtained in the same manner as in the Example 3-53 except that the resin (3-24) was used instead of the resin (3-3) used in the Example 3-53.

Preparation of mixed black curable compositions of titanium-black pigments of Examples 3-55 and 3-56

(Preparation of red pigment dispersion)

The following composition was subjected to fine dispersion treatment for 4 hours using a 0.3 mm zirconia bead using a dispersing machine (trade name: DISPERMAT, manufactured by VMA-GETZMANN GMBH) to obtain a red pigment dispersion.

̇Organic pigment: C.I. Pigment Red 254 30 parts

Neodymium resin solution (benzyl methacrylate / methacrylic acid / hydroxyethyl methacrylate copolymer, molar ratio: 80 / 10/10, Mw: 10000, resin solid content concentration: 40% of PGMEA Solution) 10 parts

̇ Solvent: 200 parts of PGMEA

̇Dispersant: 30% solution of resin (3-3) in PGMEA 30 parts

(Preparation of a hardening composition)

A black curable composition was prepared in the same manner as in Example 3-1 except that 20 parts of the titanium black dispersion obtained by using the resin (3-3) was used in the dispersion of the composition (3-III). Mixture with 4 parts of red pigment dispersion. Note that the resin (3-3) was used in Example 3-55, and the resin (3-24) was used in Example 3-56.

Preparation of black curable composition using titanium black using Comparative Examples 3-1 and 3-2

The black hardenable compositions of Comparative Example 3-1 and Comparative Example 3-2 were prepared in the same manner as in Example 3-1 except that the resin (3-1) used in Example 3-1 was changed to The resin (3-47) or the resin (3-48) obtained in the synthesis example was compared.

Preparation of the black curable composition using carbon black of Comparative Example 3-3

The black curable composition of Comparative Example 3-3 was prepared in the same manner as in Example 3-1 except that the titanium black used in Example 3-1 was changed to carbon black (TOKA BLACK 7400 (trade name), Manufactured by Tokai Carbon Co., Ltd., average primary particle diameter: 28 nm).

The specific resins or comparative resins, alkali-soluble resins and polymerization initiators used in the black curable compositions of Examples 3-1 to 3-56 and Comparative Examples 3-1 to 3-3 are shown in Tables 10 and 11.

The polymerization initiators (I-1) to (I-6) used in Examples 3-1 to 3-56 and Comparative Examples 3-1 to 3-3 were the same as those used in the examples of the first aspect of the present invention.

[Preparation and evaluation of light-shielding color filters for solid-state photographic elements]

(Step of forming a black curable composition layer)

The number of coating rotations of the spin coating was adjusted so that the film thickness was 2.0 μm after the coating/heat treatment, and the various black curable compositions of Examples 3-1 to 3-56 and Comparative Examples 3-1 to 3-3 were used. It was uniformly coated on a tantalum wafer (substrate), and heat-treated at a surface temperature of 120 ° C for 120 seconds on a hot plate. Thus, a black curable composition layer having a film thickness of 2.0 μm was obtained.

(exposure step)

Next, using an i-ray stepper exposure apparatus FPA-3000 iS+ (manufactured by Canon Inc.), via a photomask for forming a 20.0 micron line-and-space pattern, at 100 mJ/cm 2 The coating obtained was irradiated (exposed) by changing the exposure amount to a range of 5000 mJ/cm 2 in a range of 50 mJ/cm 2 .

(development step)

After irradiation (exposure), mixed-type development was carried out at 23 ° C for 60 seconds using a 0.3% aqueous solution of tetramethylammonium hydroxide (TMAH), and then rinsed with pure water for 20 seconds using a rotary sprinkler, and then pure Water washing.

Thereafter, the adhered water droplets were removed with high-grade air, and the substrate was dried to obtain a black image pattern (20.0 micron line and gap pattern).

Thereby, a light-shielding color filter for a solid-state imaging element is obtained.

[assessment]

The various black curable compositions obtained as described above and various light-shielding color filters for solid-state photographic elements were evaluated in the following manner. The evaluation results are summarized in Table 12 and Table 13.

(storage stability)

The black curable composition was made into a solution, and measured at 25 ° C for 1 day and 1 month using an E-type viscometer (TV-22 type viscometer cone-and-plate type, manufactured by Toki Sangyo Co., Ltd.). Post-viscosity (storage temperature: 10 ° C), and the difference was regarded as storage stability. The smaller the difference in viscosity, the better the storage stability.

(Evaluating substrate adhesion)

The minimum exposure amount from the substrate peeling in the SEM observation was evaluated as the sensitivity. The smaller the value of the sensitivity, the higher the adhesion of the substrate.

(Evaluating shading characteristics)

Using the obtained light-shielding color filter, the maximum transmittance in a wavelength range of 400 nm to 800 nm was measured with a spectrophotometer (UV23600, manufactured by Shimadzu). The smaller the value, the better the result. A condition in which the maximum transmittance is less than 1% indicates that the light shielding property is good.

As can be seen from Tables 12 and 13, the black curable composition of the present invention has good storage stability, substrate adhesion, and excellent light-shielding properties.

Examples 3-57 to 3-117 and Comparative Examples 3-4 to 3-6: Preparation and Evaluation of a Light-Shielding Film for Wafer Level Lenses

A resin film is formed using a curable composition for a lens film by the following procedure.

This resin film was used and a simulation evaluation was performed on the adhesion between the black curable composition and the lens.

(Forming a thermosetting resin film for a lens film)

Only the component of the component 2 shown in the row of the component 2 shown in Table 14 was added to the component 1 to prepare the curable compositions 3-1 to 3-6 for the lens film. The hardening composition for the lens film of component 2 is blank using only component 1.

The sclerosing compositions 3-1 to 3-4 (2 ml) shown in Table 14 were applied to a 5 cm × 5 cm glass substrate (thickness 1 mm, BK7, manufactured by Schott Glass Technologies, Inc.). Heating at 200 ° C for 1 minute and hardening to form a lens film (films 1 to 4) can be evaluated for the residue on the lens.

(Formation of a photocurable resin film for a lens film)

The sclerosing compositions 3-5 and 3-6 (2 ml) shown in Table 14 were applied to a 5 cm x 5 cm glass substrate (thickness 1 mm, BK7 (trade name), by Schott Glass Technologies, Inc. It was fabricated and cured with a metal halide lamp at 3000 mJ/cm 2 to form a lens film (films 3-5 and 3-6) which was evaluated for the residue on the lens.

(Forming a black curable composition layer on the lens)

The number of coating rotations of the spin coating was adjusted so that the film thickness was 2.0 μm after coating/heat treatment, and the black hardening compositions (B3- used in Examples 3-1 to 3-56 and Comparative Examples 1 to 3) were used. 1) to (B3-59) uniformly coated on the glass wafer substrate on which the resin film has been formed, which is formed of the curable compositions 3-1 to 3-6 for the lens film, and Heat treatment was carried out on a hot plate at a surface temperature of 120 ° C for 120 seconds. Thus, a black curable composition layer having a film thickness of 2.0 μm was obtained. Further, the hardenable compositions 3-1 to 3-6 and the black curable compositions (B3-1) to (B3-59) used for the lens film used in the respective examples and comparative examples are shown in Table 15 and Table 16. in.

(exposure step)

Subsequently, using a high pressure mercury lamp, changing the exposure amount by a mask having a pattern of 10 mm holes, in the range of 100 mJ/cm 2 to 1000 mJ/cm 2 , at a range of 50 mJ/cm 2 The obtained black curable composition layer was exposed.

(development step)

The exposed black curable composition layer was subjected to mixed development using a 0.3% aqueous solution of tetramethylammonium hydroxide at 23 ° C for 60 seconds, followed by rinsing with a rotary water jet, and then washed with pure water to obtain a pattern. Shaped light-shielding film.

Forming a black curable composition layer on the glass wafer on which the resin film obtained by using the curable composition of the lens film is formed, and performing exposure/development/rinsing, and using the same The obtained substrate having a light-shielding film was evaluated. The evaluation results are summarized in Tables 15 and 16.

(evaluating the adhesion on the lens)

The minimum exposure amount at which the resin film obtained by using the curable composition of the lens film was not peeled off was evaluated as an index of adhesion to the lens. The smaller the value of the minimum exposure, the higher the adhesion to the lens.

(Forming a black curable composition layer on a glass wafer)

The coating rotation number of the spin coating was adjusted so that the film thickness was 2.0 μm after the coating/heat treatment, and the black curable compositions (B3-1) to (B3-59) were uniformly applied to the glass wafer substrate ( The thickness was 1 mm, BK7, manufactured by Schott Glass Technologies, Inc., and heat treatment was performed on a hot plate at a surface temperature of 120 ° C for 120 seconds. Thus, a black curable composition layer having a film thickness of 2.0 μm was obtained.

(exposure step)

Subsequently, using a high pressure mercury lamp, through a reticle having a 5 mm hole pattern, changing the exposure amount in the range of 100 mJ/cm 2 to 1000 mJ/cm 2 at 50 mJ/cm 2 to The obtained coating was exposed.

(development step)

The exposed black curable composition layer was subjected to mixed development using a 0.3% aqueous solution of tetramethylammonium hydroxide at 23 ° C for 60 seconds, followed by rinsing with a rotary water jet, and then washing with pure water to obtain A light-shielding film of a pattern shape.

(Evaluating adhesion to glass wafers)

A black curable composition layer was formed on the glass wafer, and exposure/development/rinsing was performed, and evaluation was performed using the obtained substrate having a light-shielding film.

The minimum exposure amount that did not appear to be peeled off from the glass wafer substrate was evaluated as an index of adhesion to the glass wafer. The smaller the value of the minimum exposure, the higher the adhesion to the glass wafer.

(Evaluating shading characteristics)

Using the obtained light-shielding color filter, the maximum transmittance in a wavelength range of 400 nm to 800 nm was measured with a spectrophotometer (UV23600, manufactured by Shimadzu). The smaller the value, the better the result. In the case where the maximum transmittance is 1% or less, it indicates that the light-shielding property is good.

The evaluation results are summarized in Tables 15 and 16.

As can be seen from Tables 15 and 16, the black curable composition of the present invention has excellent adhesion to lenses (which is especially important for wafer level lens applications) and also has excellent adhesion to glass wafer substrates.

As can be seen from the above description, the black curable composition of the present invention has excellent adhesion to the germanium wafer under exposure exposure using an i-ray stepper exposure apparatus, and the exposure apparatus is used for the shading property of the solid-state imaging element. Necessary during film formation, and under irradiation with mercury lamps The lens and the glass substrate have very good adhesion, which is necessary for the formation of a light-shielding film for wafer level lenses.

<Example 3-118>

The curable resin layer 5 is formed on the glass substrate using the curable composition 5 of the lens film, and its shape is transcribed into a quartz mold having a lens shape, and hardened by a high pressure mercury lamp at an exposure amount of 3000 mJ/cm 2 . Forming a lens. Next, the black curable composition (B3-1) of Example 3-1 was applied, and exposed with a high pressure mercury lamp, through a reticle having a 0.5 mm hole pattern, and moved with a 0.3% aqueous solution of tetramethylammonium hydroxide. In addition to the unexposed portions, a light-shielding film is formed at the outer and outer edges of the lens to form a wafer-level lens array having a plurality of wafer-level lenses.

The wafer level lens array obtained is cut, and a lens module is formed therefrom, and then the photographic element and the sensor substrate are assembled to form a photographic unit.

The wafer-level lens obtained in Example 3-118 has no residue at the opening of the lens and has good transmittance, and is highly uniform in one portion of the light-shielding layer on the coated side, and no opaque section is observed. Peeled and has high light blocking properties.

Examples 3-119 to 3-172 and Comparative Examples 3-7 to 3-9: Preparation and Evaluation of Infrared Films for Solid-State Photographic Elements

<Manufacturing substrate A and substrate B>

(Manufacture of substrate A)

Substrate A was fabricated in the following manner to verify the development residue in the solid-state photographic element (in the form of no solder resist layer on the back side) of one of the embodiments described above.

That is, a circle made of copper (Cu) having a thickness of 5 μm and a diameter of 10 μm is obtained on a substrate having a thickness of 1000 μm by micromachining (photolithography), sputtering, and electroplating techniques. Shaped metal electrode.

Therefore, as shown in the schematic cross-sectional view of FIG. 11, the substrate A having the plurality of circular metal electrodes 310 is obtained on the ruthenium substrate 300.

(Manufacture of substrate B)

The substrate B was fabricated in the following manner to verify the development residue in the solid-state photographic element (in the form of a solder resist layer on the back side) of one of the embodiments described above.

A solder resist having a pattern shape is formed on the side of the circular metal electrode on which the substrate A has been formed by photolithography using the following solder resist.

As the pattern of the solder resist layer, a pattern having an opening exposing a part of the metal electrode as shown in Fig. 13 was employed.

Therefore, as shown in the schematic cross-sectional view of FIG. 13, the substrate B having the configuration of the circular metal electrode 310 and the solder resist layer 330 is obtained on the ruthenium substrate 300.

The components of the solder resist are as follows.

̇The following resin solution 155 parts

2-(Ethyloxyiminomethyl)thioxan-9-one (photopolymerization initiator) 2 parts

2-Methyl-1-[4-(methylthienyl)]-2-(N-morpholinyl)propan-1-one (photopolymerization initiator) 6 parts

̇2,4-diethyl-9-thioxanthene (sensitizer) 1 part

̇C.I. Pigment Blue 15:6 (colorant) 0.9 parts

̇C.I. Pigment Yellow 199 (colorant) 2.3 parts

Diisopentaerythritol hexaacrylate (monomer) 20 parts

Trimethylolpropane triacrylate (monomer) 10 parts

Barium sulfate (filler) 130 parts

Phenolic phenol varnish type novolac epoxy resin (EPPN-201, manufactured by Nippon Kayaku Co., Ltd.) (thermosetting component) 15 parts

Co-linked xylenol epoxy resin (YX-4000, manufactured by Epoxy Resins Co., Ltd.) 30 parts

̇ Melamine 3 parts

Dipropylene glycol methyl ether acetate 5 parts

̇#150 (aromatic organic solvent, manufactured by Idemitsu Petrochemical Co., Ltd.) 5 parts

(Preparation of resin solution)

First, 660 g of cresol novolak type epoxy resin (EOCN-104S, manufactured by Nippon Kayaku Co., Ltd.), 421.3 g of carbitol acetate, and 180.6 g of solvent petroleum spirit were fed, followed by 90 ° C. Heat / stir to dissolve. Next, the mixture was cooled to 60 ° C, and 216 g of acrylic acid, 4.0 g of triphenylphosphine, and 1.3 g of p-methoxyphenol were added thereto, followed by a reaction at 100 ° C for 12 hours. At this time, the acid value was 0.3 mgKOH/g. Add 241.7 public to it Tetrahydrophthalic anhydride was then heated to 90 ° C and the reaction was allowed to proceed for 6 hours. Thus, a solid content concentration of 65% by mass, a solid content of 77 mg KOH/g, and a double bond equivalent (resin weight per gram of unsaturated groups (g)) of 400 g/eq were obtained. And a resin solution having a weight average molecular weight of 8,000.

<Manufacture of a light-shielding film>

The black curable composition prepared above was spin-coated on the side of the substrate A on which the metal electrode was formed, and then heated on a hot plate at 120 ° C for 2 minutes to obtain a black curable composition coating.

Next, using an i-ray stepper exposure apparatus, each having an exposure of 100 mJ/cm 2 , 200 mJ/cm 2 , 300 mJ/cm 2 , 400 mJ/cm 2 , and 500 mJ/cm 2 The resulting coating was subjected to pattern exposure.

Subsequently, the exposed coating layer was subjected to mixed development using a 0.3% aqueous solution of tetramethylammonium hydroxide at 23 ° C for 60 seconds, followed by rinsing with a rotary water jet, and then washing with pure water to obtain a patterned shape. A light-shielding film.

A light-shielding film having an opening pattern is formed herein, the opening exposing a portion of the metal electrode 310 as shown in FIG. 12 (the light-shielding film 320 in FIG. 12).

Thus, a light-shielding film having a pattern shape is formed in the same manner (except that the substrate B is used instead of the substrate A).

A light-shielding film having an opening pattern is formed herein, the opening exposing a portion of the metal electrode 310 as shown in FIG. 14 (specifically, when viewed in a direction perpendicular to the substrate, the pattern overlaps with the solder resist layer; FIG. 14 The light-shielding film 340).

(evaluating adhesion)

For the SEM observations, the minimum exposure amount without peeling was evaluated as sensitivity. The smaller the value of the sensitivity, the higher the adhesion of the substrate.

(Evaluating shading characteristics)

Using the obtained light-shielding color filter, the maximum transmittance in the wavelength region of 800 nm to 1200 nm was measured with a spectrophotometer (UV23600, manufactured by Shimadzu). The smaller the value, the better the result. A condition in which the maximum transmittance is less than 1% indicates that the light shielding property is good.

The results are shown in Tables 17 and 18.

Table 17

As is apparent from the results in Tables 17 and 18, the infrared-shielding film of the present invention exhibits high adhesion to any of copper and solder resist layers as metal electrodes.

10‧‧‧Substrate

12‧‧‧ lens/concave lens

14‧‧‧ opaque film

Claims (19)

A black curable composition comprising: (A3) an inorganic pigment; (B3) a chain-like resin comprising a solvent-compatible portion and a pigment-adsorbing portion having an acid group, wherein the chain-like resin is a block polymer; (C3) a polymerization initiator; and (D3) a polymerizable compound. The black curable composition according to claim 1, wherein the (A3) inorganic pigment comprises titanium black. The black curable composition according to claim 1, wherein the solvent compatibility portion comprises a repeating unit having a content of 80% by mass or more and an I/O value of 0.05 to 1.50. The black curable composition according to claim 1, wherein the solvent compatibility portion comprises a repeating unit represented by the following formula (IA) or the following formula (IB): Wherein, in the formula (IA), R ¹ represents an alkoxy group, a cycloalkoxy group or an aryloxy group; and R ² represents a hydrogen atom, a halogen atom or an alkyl group; Wherein, in the formula (IB), R ³ represents an aryl group; and R ⁴ represents a hydrogen atom or an alkyl group. The black curable composition according to claim 1, wherein the (C3) The polymerization initiator is an oxime ester compound or a hexaarylbiimidazole compound. The black curable composition according to claim 1, further comprising (E3) an alkali-soluble resin in addition to the (B3) chain resin. The black curable composition according to claim 1, which further comprises (F3) an organic pigment. The black curable composition according to claim 1, wherein a mass ratio of the solvent-compatible portion to the pigment-adsorbing portion in the (B3) chain resin (solvent-compatible portion) : Pigment adsorption moiety) is from 90:10 to 40:60. The black curable composition according to claim 1, wherein the (B3) chain resin has a PQ structure comprising a structural unit formed of a plurality of Ps and a structural unit formed of a plurality of Qs. Or a PQP type structure comprising two structural units each formed of a plurality of P and a structural unit formed of a plurality of Q, P represents a solvent compatible portion, and Q represents a pigment adsorbing moiety and has an acid group. The (B3) chain resin has an acid value of 50 mgKOH/kg to 150 mgKOH/g, and the solvent compatibility portion has an acid value of 0 mgKOH/kg to 20 mgKOH/g. The black curable composition according to claim 1, wherein the (B3) chain resin has a PQ structure comprising a structural unit formed of a plurality of Ps and a structural unit formed of a plurality of Qs. Or a PQP type structure comprising two structural units each formed of a plurality of P and a structural unit formed of a plurality of Q, P represents a solvent compatible portion, and Q represents a pigment adsorbing moiety and has an acid group. The (B3) chain resin has an amine value of 50 mgKOH/g to 150 mgKOH/g, and the solvent-compatible portion has an amine value of 0 mgKOH/g. The black curable composition according to any one of claims 1 to 10, which is used for forming an infrared ray blocking film, which blocks infrared light and is provided on a ruthenium substrate. On one surface. A black curable composition for a solid-state photographic element, which comprises the black curable composition according to any one of claims 1 to 10. A light-shielding color filter for a solid-state photographic element, which comprises the black curable composition as described in claim 12 of the patent application. A solid-state photographic element comprising the same as described in claim 13 A light-shielding color filter of a photographic element. A black curable composition for a wafer level lens, comprising the black curable composition according to any one of claims 1 to 10. A wafer-level lens comprising a light-shielding film obtained by using a black curable composition as described in claim 15 in a peripheral portion of a lens present on a substrate. An infrared ray-blocking film which is formed on a ruthenium substrate having a photographic element section on a surface opposite to a surface on which the photographic element is provided, using the black curable composition as described in claim 11 of the patent application. A method for producing an infrared ray-blocking film, comprising: applying a black curable composition as described in claim 11 to a ruthenium substrate having a photographic element segment and provided thereon Forming a photosensitive layer on a surface opposite to the surface of the photographic element; patterning the photosensitive layer; and developing the exposed photosensitive layer to form a pattern. A solid-state photographic element comprising the infrared ray-blocking film according to claim 17, wherein the opaque film is provided on a ruthenium substrate having a photographic element segment and the photographic element is provided thereon The surface is opposite to the surface.